Liquid crystalline compound, liquid crystal composition comprising the liquid crystal-line compound, and liquid crystal display device using the liquid crystal composition

ABSTRACT

The invention is to provide liquid crystalline compounds which have a low viscosity, high negative dielectric anisotropy, high resistivity, and high voltage holding ratio, and are stable against heat and ultraviolet light; to provide liquid crystal compositions comprising the liquid crystalline compound; and to provide liquid crystal display devices using the liquid crystal composition therein; 
     the liquid crystalline compound is expressed by the general formula (1)                    
      wherein R 1  and Y 1  represent an alkyl group having 1 to 20 carbon atoms; X 1 , X 2 , and X 3  independently represent single bond, 1,2-ethylene group, vinylene group, —COO—, —CF 2 O—, or —OCF 2 —; ring A 1 , ring A 2 , ring A 3 , and ring A 4  independently represent trans-1,4-cycloliexylene, or 1,4-phenylene hydrogen atom on the ring may be replaced by fluorine atom or chlorine atom provided that at least one of ring A 2 , ring A 3 , and ring A 4  represents 2,3-difluoro-1,4-phenylene; m and n are 0 or 1, and each element which constitutes this compound may be replaced by its isotope.

This application is a continuation of Ser. No. 09/155,595 filed Sep. 30,1998, now Pat. No. 6,190,576 which is a 371 application ofPCT/JP97/01048 filed Mar. 27, 1997.

TECHNICAL FIELD

The present invention relates to novel liquid crystalline compoundswhich make liquid crystal compositions principally for twist nematic(TN) display modes super twist nematic (STN) display mode, or thin filmtransistor (TFT) display mode develop preferable physical properties, toliquid crystal compositions comprising the liquid crystalline compoundand having preferable physical properties, and to liquid crystal displaydevices using the liquid crystal composition therein.

BACKGROUND ART

Liquid crystal display devices utilize optical anisotropy and dielectricanisotropy of liquid crystal substances. The liquid crystal displaydevices are widely used in tabletop calculators, word processors, andtelevision sets, including watches, and demand for the display devicesis in a trend to increase year by year. Liquid crystal phase existsbetween solid phase and liquid phase, and is divided broadly intonematic phase, smectic phase, and cholesteric phase. Among them, nematicphase is most widely employed for display devices at present. On theother hand, while many display modes were devised up to date, threetypes of twist nematic (TN) mode, super twist nematic (STN) mode, andthin film transistor (TFT) mode have now become main currents.Properties required of liquid crystal substances (liquid crystallinecompounds) for these various liquid crystal display devices aredifferent depending on their uses, but any of the liquid crystalsubstances is required to be stable against outside environmentalfactors such as moisture, air, heat, and light; to exhibit liquidcrystal phase at a temperature range as wide as possible with roomtemperature being its center; to be in a low viscosity; and to have alow driving voltage. However, no liquid crystal substances which satisfysuch requirements at the same time by a single compound have been found.

With respect to liquid crystal substances used for liquid crystaldisplay devices, it is an actual circumstance that several kind orseveral tens kind of liquid crystalline compounds, and further severalkind of liquid non-crystalline compounds when necessary, are usuallymixed to produce liquid crystal compositions and used for displaydevices, in order to adjust such physical properties as dielectricanisotropy (Δ∈), optical anisotropy (Δn), viscosity, and elasticconstant ratio K₃₃/K₁₁ (K₃₃: bend elastic constant, K₁₁: splay elasticconstant) of liquid crystal compositions to most suitable ones requiredof each display device. Accordingly, liquid crystalline compounds arerequired to be excellent in miscibility with other liquid crystalcompounds, and recently in particular required to be excellent in themiscibility even at low temperatures from the requirement of being usedin various environments.

Meanwhile, active matrix mode, especially thin film transistor (TFT)mode is extensively adopted in recent years as display mode, forexample, for television sets and viewfinders from the aspect of displayperformances such as contrast, display capacity, and response time.Also, STN mode which has a large display capacity and display devices ofwhich can be produced by comparatively simpler methods and at a lowercost than those of active matrix mode from the structural factor ofdisplay devices is largely adopted in displays, for example, forpersonal computers.

Recent development in these fields is being progressed while placingstress on

(a) downsizing of liquid crystal display devices into a portable size asshown by the development of small size TV sets and notebook sizepersonal computers both of which are characterized by being in smallsize, light, and thus portable; and

(b) production of liquid crystalline compounds and liquid crystalcompositions having a low driving voltage, that is, a low thresholdvoltage from the viewpoint of withstand voltage of IC, in the aspect ofliquid crystal material.

It is known that threshold voltage (Vth) can be expressed by thefollowing equation (H. J. Deuling et al., Mol. Cryst. Liq. Cryst., 27(1975) 81):

V_(th)=π(K/∈₀Δ∈)^(½)

In the equation described above, K is an elastic constant and ∈₀ is adielectric constant in vacuum. As will be seen from this equation, twomethods, that is, a method of increasing dielectric anisotropy (Δ∈) anda method of lowering elastic constant can be considered to lower thethreshold voltage. However, since actual control of elastic constant isvery difficult, it is an actual situation that liquid crystal materialshaving a high dielectric anisotropy (Δ∈) are ordinarily used to copewith the requirements. With the facts described above for a background,development of liquid crystalline compounds having a high dielectricanisotropy (Δ∈) has actively been conducted.

Almost all liquid crystal compositions currently used in display devicesfor TFT mode are composed of fluorine type liquid crystal materials.This is because (i) a high voltage holding ratio (V.H.R.) is required inTFT mode from the viewpoint of construction of the devices, (ii) thematerials have to be small in the temperature dependency, and (iii)materials other than fluorine type can not meet these requirements. Asfluorine type materials for low voltage, the following compounds areheretofore disclosed:

in the structural formula described above, R represents an alkyl group.

Whereas it is reported that either compounds (a) and (b) have severalfluorine atoms at a terminal of the molecule and exhibit a highdielectric anisotropy, it is known that their clearing point (NI point)is low and viscosity is a comparatively high. Among the persons skilledin the art, it is empirically known that there are inverselyproportional and direct proportional relations between the number ofsubstituted fluorine atom and the clearing point, and between the numberof substituted fluorine atom and the viscosity, respectively, althoughit is not simple. Accordingly, it is difficult to attain the requiredclearing point and viscosity (response speed) when liquid crystalcompositions are produced only a series of these compounds. With theobject of offsetting this defect, a viscosity decreasing agentrepresented by the following compounds is usually added in liquidcrystal compositions.

in the structural formula described above, R and R′ represent an alkylgroup.

Whereas compounds (c) have a comparatively low viscosity, their clearingpoint is not sufficiently high to offsetting the low clearing point ofliquid crystal compositions comprising the liquid crystalline compoundsfor low voltage described above. In order to meet the requirement, acomparatively large amount is necessary to be added, but characteristicsof liquid crystal compositions are lost in this case. Accordingly,compounds (c) are unsuitable as material to solve the problems describedabove. Whereas compounds (d) have a sufficiently high clearing point,their viscosity is remarkably high since they have a four ringstructure. Thus, the increase in the viscosity is unavoidable when thecompounds (d) are added in liquid crystal compositions. Besides, sincecompounds (d) themselves have smectic phase, when liquid crystalcompositions prepared by adding the compounds were left at a lowtemperature, smectic phase some times develops in the liquid crystalcompositions. is Accordingly, compounds (d) are unsuitable to solve theproblems described above, either. Further, since any one of compounds(c) and (d) has an extremely low dielectric anisotropy value, when it isadded to liquid crystal compositions for low voltage having a largedielectric anisotropy value as described above, the compoundconsiderably lower the dielectric anisotropy of the liquid crystalcompositions. As the result, the threshold voltage of the compositionsraise, and thus, the compound is not preferable to solve the problems.

In the meantime, researches to overcome narrow viewing angle which isonly one defect of liquid crystal panel of TFT display mode wereactively conducted recent years, and many results of the researches arereported at lectures in academic society and disclosed in patentpublications. As an example of the step for the improvement, thefollowing method is disclosed. For instance, in Laid-open JapanesePatent Publication Nos. Hei 4-229828 and Hei 4-258923, a method isdisclosed in which the viewing angle is improved by disposing a phasedifference film between a pair of polarizing plates and a TN type liquidcrystal cell. In Laid-open Japanese Patent Publication Nos. Hei 4-366808and Hei 4-366809, a method is disclosed in which two layers liquidcrystal system using a layer of chiral nematic liquid crystal as phasedifference film is adopted. However, either methods described above areinsufficient in improvement of the viewing angle and also had suchproblems that production cost is high and liquid crystal panels becomeheavy.

As a new method to solve the problems, In-Plane Switching (IPS) drivinghas recently come to attract public attention (R. Kiefer et al., JAPANDISPLAY '92, 547 (1992); G. Baur, Freiburger ArbeitstagungFlussigkristalle, Abstract No. 22 (1993)). As characteristics in thestructure of liquid crystal panels of the IPS drive, the fact thatwhereas an electrode is disposed on both upper and lower substrates,respectively, in conventional liquid crystal panels, a comb-shapeelectrode is disposed on the substrate only at one side in the IPSdrive, and the fact that the direction of major axis of liquid crystalmolecules is all the time in parallel to the substrates in the IPS drivecan be mentioned. As advantages of the IPS drive,

{circle around (1)} cell thickness can be reduced since the electrodeexists on the substrate only at one side,

{circle around (2)} reduction of production cost can be expected sincecell thickness can be reduced, and

{circle around (3)} distance between electrodes is maintained constant,can be mentioned in addition to the fact that the viewing angle isexpanded.

In order to actualize high speed response and low voltage drive in theIPS drive, the liquid crystalline compounds to be used are required tohave a low viscosity and a high negative dielectric anisotropy. Also, asanother example of attempts to improve the narrow viewing angle, amethod which utilizes a vertical orientation of liquid crystal moleculesand is disclosed in Laid-open Japanese Patent Publication No. Hei2-176625 can be mentioned. One of the characteristics of this method isthe use of liquid crystal compositions having a negative dielectricanisotropy. Meantime, as a conventional compound having a high negativedielectric anisotropy, the following compounds are disclosed in thepatent publication shown below:

in the structural formula described above, R represents an alkyl group.

Compounds (e) (Japanese Patent Publication No. Sho 61-26899) arereported to have 2,3-dicyano-1,4-phenylene group in their partialstructure and exhibit a high negative anisotropy. However, since theyhave cyano groups, their dependency of voltage holding ratio ontemperature is large and viscosity is remarkably high, and thus thecompounds can not be used as liquid crystal material for IPS driveutilizing TFT display mode. As described above, compounds havingcharacteristics which are necessary for actualizing the high speedresponse and low voltage driving in the IPS driving, in a well balancedcondition with each other, have not yet been known.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide liquid crystallinecompounds which have such a high resistivity and high voltage holdingratio as can be used even for TFT display mode, are stable against heatand UV irradiation, have an effect as viscosity reducing agent, that is,

1) effect of raising clearing point of liquid crystal compositions,

2) effect of reducing viscosity of the compositions, and

3) effect of preventing the dielectric anisotropy of the compositionsfrom lowering (or preventing the threshold voltage of the compositionsfrom raising), in a comprehensively well balanced condition, and furtherhave a low viscosity and high negative dielectric anisotropy which cancope with the IPS driving or with such display devices of verticallyoriented mode as described in Laid-open Japanese Patent Publication No.Hei 2-176625; to provide liquid crystal compositions comprising theliquid crystalline compound; and to provide liquid crystal displaydevices fabricated by using the liquid crystal composition.

Heretofore, as for the compounds which have a partial structure in whichtwo phenylene groups are cross-linked with bonding group —CF₂O— and havean alkyl group as both terminal groups of the molecule, structuralformula is disclosed in Laid-open Japanese Patent Publication No. Hei2-289529 only with reference to two rings compound (f). It is true thatstructural formula is described in the patent publication mentionedabove. However, physical data of the compound and specific value ofphysical properties of the compound necessary for evaluating the utilityas liquid crystalline compound are not disclosed at all, and thus thecharacteristics of the compound were not known in the least.

Then, specific two rings, three rings, or four rings compounds whichhave a partial structure in which two ring structures are cross-linkedwith bonding group —CF₂O— and have a group selected from an alkyl group,alkenyl group, alkoxy group, alkoxyalkyl group, and alkynyl group asboth terminal groups of the molecule were devised and their physicalproperties were diligently investigated by the present inventors to findout that the compounds have not only a high clearing point but also anextremely low viscosity lower than expected at first, that the compoundsexhibit a medium extent of dielectric anisotropy value (Δ∈=˜4.0), andfurther that the compounds having a partial structure of2,3-difluoro-1,4-phenylene group and a bonding group of —COO—, —CF₂O—,or —OCF₂— at the same time not only exhibit a large negative dielectricanisotropy value but also are excellent in miscibility with other liquidcrystal compounds, have a high resistivity and high voltage holdingratio, and are stable physically and chemically, leading to theaccomplishment of the present invention.

Thus, the present invention is summarized as shown in the followingparagraphs [1] to [29]:

[1]A liquid crystalline compound expressed by the general formula (1)

wherein R¹ and Y¹ represent an alkyl group having 1 to 20 carbon atomsone or more non-adjacent methylene groups in the alkyl group may bereplaced by oxygen atom, sulfur atom, or vinylene group, and one or morehydrogen atoms in the alkyl group may be replaced by fluorine atom orchlorine atom;

X¹, X², and X³ independently represent single bond, 1,2-ethylene group,vinylene group, —COO—, —CF₂O—, or —OCF₂— provided that at least one ofX¹, X², and X³ represents —COO—, —CF₂O—, or —OCF₂—;

ring A¹, ring A², ring A³, and ring A⁴ independently representtrans-1,4-cyclohexylene group CH₂ group on which ring may be replaced byoxygen atom, or 1,4-phenylene group one or more hydrogen atoms of whichmay be replaced by fluorine atom or chlorine atom; and m and n are 0 or1

provided that when X¹, X², or X³ represents —COO—, then at least one ofring A², ring A³, and ring A⁴ represents 2,3-difluoro-1,4-phenylenegroup, and Y¹ represents an alkoxy group;

when m=n=0 and X¹ represents —COO—, then ring A¹ represents1,4-phenylene group at least one hydrogen atom in which group isreplaced by fluorine atom;

when m=1, n=0, X¹ represents single bond or 1,2-ethylene group, and X²represents —COO—, then ring A² represents 1,4-phenylene group at leastone hydrogen atom in which group is replaced by fluorine atom;

when m=n=1, X² represents —COO—, and X¹ represents single bond or1,2-ethylene group, then ring A² represents 1,4-phenylene group at leastone hydrogen atom in which group is replaced by fluorine atom;

when m=n=1, X³ represents —COO—, and X¹ and X² independently representsingle bond or 1,2-ethylene group, then ring A³ represents 1,4-phenylenegroup at least one hydrogen atom in which group is replaced by fluorineatom; and

when m=n=0 and X¹ represents —CF₂O— or —OCF₂—, then ring A¹ or ring A⁴represents trans-1,4-cyclohexylene group, or 1,4-phenylene group atleast one hydrogen atom in which group is replaced by chlorine atom orfluorine atom when m+n=1, X² or X³ represents —CF₂O—, ring A² or ring A³represents 1,4-phenylene group, and A⁴ represents 1,4-phenylene group atleast one hydrogen atom in which group may be replaced by a halogenatom, then Y¹ represents an alkyl or alkoxy group, and

each element which constitutes this compound may be replaced by itsisotope.

[2] The liquid crystalline compound recited in paragraph [1] abovewherein m=n=0, X¹ is —CF₂O—, and ring A¹ or ring A⁴ is 1,4-phenylenegroup at least one hydrogen atom in which group is replaced by fluorineatom or chlorine atom in the general formula (1).

[3] The liquid crystalline compound recited in paragraph [1] abovewherein m=1, n=0, and X² is —COO— in the general formula (1).

[4] The liquid crystalline compound recited in [1] above wherein m=n=1and X² is —COO—in the general formula (1).

[5] The liquid crystalline compound recited in paragraph [1] abovewherein m=n=1 and X³ is —COO— in the general formula (1).

[6] The liquid crystalline compound recited in paragraph [3] abovewherein ring A¹ is trans-1,4-cyclohexylene group and ring A² is1,4-phenylene group in the general formula (1).

[7] The liquid crystalline compound recited in paragraph [3] abovewherein both ring A¹ and ring A² are trans-1,4- cyclohexylene group inthe general formula (1).

[8] The liquid crystalline compound recited in paragraph [6] abovewherein X¹ is 1,2-ethylene group, X² is —COO—, and ring A² is3-fluoro-1,4-phenylene group in the general formula (1).

[9] The liquid crystalline compound recited in paragraph [6] abovewherein X¹ is vinylene group and X² is —COO— in the general formula (1).

[10] The liquid crystalline compound recited in paragraph [7] wherein X¹is vinylene group and X² is —COO— in the general formula (1).

[11] The liquid crystalline compound recited in paragraph [1] abovewherein m=1, n=0, and X¹ or X² is —CF₂O— or —OCF₂— in the generalformula (1).

[12] The liquid crystalline compound recited in paragraph [11] abovewherein both R¹ and Y¹ are an alkyl group in the general formula (1).

[13] The liquid crystalline compound recited in paragraph [11] abovewherein at least one of R¹ and Y¹ is an alkenyl group in the generalformula (1).

[14] The liquid crystalline compound recited in paragraph [11] abovewherein X¹ is single bond, X² is —CF₂O— or —OCF₂—, both ring A¹ and ringA² are 1,4-cyclohexylene group, and ring A⁴ is 1,4-phenylene group atleast one hydrogen atom of which may be replaced by fluorine atom orchlorine atom in the general formula (1).

[15] The liquid crystalline compound recited in paragraph [1] abovewherein m=n=1, and X¹, X², or X³ is —CF₂O— or OCF₂— in the generalformula (1).

[16] The liquid crystalline compound recited in paragraph [15] abovewherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are1,4-cyclohexylene group, both ring A² and ring A³ are 1,4-phenylenegroup at least one hydrogen atom of which may be replaced by fluorineatom or chlorine atom, X² is —CF₂O— or —OCF₂—, and both X¹ and X³ aresingle bond in the general formula (1).

[17] The liquid crystalline compound recited in paragraph [15] abovewherein R¹ and Y¹ are an alkyl group, both ring A¹ and ring A⁴ are1,4-cyclohexylene group, both ring A² and ring A³ are 1,4-phenylenegroup at least one hydrogen atom of which may be replaced by fluorineatom or chlorine atom, X² is —CF₂O— or —OCF₂—, and any one of X¹ and X³is single bond and the other is 1,2-ethylene group in the generalformula (1).

[18] The liquid crystalline compound recited in paragraph [15] abovewherein at least one of R¹ and Y¹ is an alkenyl group in the generalformula (1).

[19] A liquid crystal composition comprising at least two components andcomprising at least one liquid crystalline compound expressed by thegeneral formula (1).

[20] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one ormore non-adjacent methylene groups in the alkyl group may be replaced byoxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may bereplaced by fluorine atom;

Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H,—CFH₂OCF₂CF₂H, or —OCF₂CFHCF₃;

L¹ and L² independently represent hydrogen atom or fluorine atom;

Z¹ and Z² independently represent 1,2-ethylene group, vinylene group,1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond;

ring B represents trans-1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or1,4-phenylene group hydrogen atom of which may be replaced by fluorineatom;

ring C represents trans-1,4-cyclohexylene, or 1,4-phenylene grouphydrogen atom of which may be replaced by fluorine atom; and

each atom which constitutes these compounds may be replaced by itsisotope.

[21] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or vinylene group, and any hydrogenatom in the alkyl group may be replaced by fluorine atom;

y³ represents CN group or —C≡C—CN;

ring D represents trans-1,4-cyclohexylene, 1,4-phenylene,pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group;

ring E represents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogenatom of which may be replaced by fluorine atom, or pyrimidine-2,5-diylgroup;

ring F represents trans-1,4-cyclohexylene or 1,4-phenylene group;

Z³ represents 1,2-ethylene group, —COO—, or single bond;

L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom;

a, b, and c are independently 0 or 1; and

each atom which constitutes these compounds may be replaced by itsisotope.

[22] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, and comprising, as a second compound, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom;

ring G, ring I, and ring J independently representtrans-1,4-cyclohexylene, pyrimidine-2,5-diyl, or 1,4-phenylene group atleast one hydrogen atom of which may be replaced by fluorine atom;

Z⁴ and Z⁵ independently represent —C≡C—, —COO—, —CH₂CH₂—, —CH═CH—, orsingle bond; and

each atom which constitutes these compounds may be replaced by itsisotope.

[23] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, and comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom;

ring K represents trans-1,4-cyclohexylene or 1,4-phenylene group;

Z⁶ and Z⁷ independently represent —CH₂CH₂—, —CH₂O—, or single bond; and

each atom which constitutes these compounds may be replaced by itsisotope.

[24] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (7), (8), and (9), and comprising, asa third component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(10), (11), and (12).

[25] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4), and comprising, asa third component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(7), (8), and (9).

[26] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby the general formula (5) or (6), and comprising, as a third component,at least one compounds selected from the group consisting of thecompounds expressed by any one of the general formulas (7), (8), and(9).

[27] A liquid crystal composition comprising, as a first component, atleast one liquid crystalline compound recited in any one of paragraphs[1] to [18] above, comprising, as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4), comprising, as athird component, at least one compound selected from the groupconsisting of the compounds expressed by the general formula (5) or (6),and comprising, as a fourth component, at least one compound selectedfrom the group consisting of the compounds expressed by any one of thegeneral formulas (7), (8), and (9).

[28] A liquid crystal composition comprising one or more opticallyactive compounds in addition to the liquid crystal composition recitedin any one of paragraphs [19] to [27] above.

[29] A liquid crystal display device using therein the liquid crystalcomposition recited in any one of paragraphs [19] to

[28] above.

Any compounds of the present invention have a high clearing point andare low in viscosity. Among them, the compounds in which2,3-difluoro-1,4-phenylene group is not selected as ring structureexhibit a medium extent of dielectric anisotropy value (Δ∈=˜4.0). On theother hand, the compounds in which 2,3-difluoro-1,4-phenylene group isselected as ring structure exhibit a large negative dielectricanisotropy value. Any type of these compounds are excellent inmiscibility with other liquid crystal compounds, have a high resistivityand high voltage holding ratio, and are stable physically andchemically.

More specifically, the compounds in which an alkyl group is selected asterminal substituents of the molecule exhibit an extremely high voltageholding ratio and are very effective as viscosity reducing agent fordisplay devices of TFT mode. The compounds in which an alkenyl group oranother one is selected as terminal group of the molecule exhibit acomparatively large elastic constant ratio and are very useful asviscosity reducing agent for display devices of STN mode.

Since the compounds in which 2,3-difluoro-1,4-phenylene group is notselected as ring structure have a medium extent of dielectric anisotropyvalue compared with the compounds (c) or (d) described in the section ofBACKGROUND ART, when the compounds are added to liquid crystalcompositions having a high dielectric anisotropy and used for lowvoltage, it is possible to raise clearing point and further to maintainor reducing viscosity while suppressing the lowering of dielectricanisotropy (raising of threshold voltage).

On the other hand, since the compounds in which2,3-difluoro-1,4-phenylene group is selected as ring structure are lowin viscosity as described above and exhibit a large negative dielectricanisotropy value, it is possible to provide liquid crystal compositionsand liquid crystal display devices which can be driven at a low voltageand can respond at a high speed in display devices of the IPS driving orthe devices of such vertically oriented mode as described in Laid-openJapanese Patent Publication No. Hei 2-176625 by using the compounds ofthe present invention.

As a matter of course, while any compounds of the present inventionexhibit preferable physical properties, liquid crystal compositionswhich meet their own purposes can be produced by using compounds inwhich proper R¹, Y¹, rings A¹, A², A³, and A⁴, X¹, X², X³, m, and n inthe general formula (1) are selected.

That is, when the compounds are used for liquid crystal compositions ofwhich temperature range of liquid crystal phase has to be at as high atemperature as possible, it is sufficient to use four rings compounds inwhich m=n=1, and when the circumstance is not so, it is sufficient touse two rings or three rings compounds.

When a particularly high voltage holding ratio is necessary, forexample, for liquid crystal compositions used in active matrix, it issufficient to select an alkyl group or alkoxy group as side chains R¹and Y¹. When a large elastic constant ratio is necessary, for example,for STN liquid crystal compositions, it is sufficient to select asubstituent having such an unsaturated bonding group as an alkenyl groupand alkynyl group as side chains R¹ and Y¹.

In order to obtain compounds having a positive comparatively largedielectric anisotropy value, it is sufficient to select compounds havinga partial structure in which two 1,4-phenylene groups are cross-linkedwith —CF₂O—, and substitute one or two fluorine atoms at the orthoposition of phenyl ring at the side of difluoromethylene. In order toanswer a still larger dielectric anisotropy value, it is sufficient toadditionally substitute one or two fluorine atoms at the meta positionon the phenyl ring at the side of oxygen atom in the fluorine atomsubstituted partial structure described above, and the purpose can beachieved by introducing fluorine atom so that the dipoles face the samedirection.

In order to obtain compounds having a large negative dielectricanisotropy value, it is sufficient to select —CF₂O— or —COO— for one ofbonding groups, X¹, X², and X³. Further, the compounds in which2,3-difluoro-4-alkoxyphenyl group is selected instead of2,3-difluoro-1,4-phenylene group exhibit a higher negative dielectricanisotropy.

Optical anisotropy value can also be optionally adjusted by selectingproper R¹, Y¹, rings A¹, A², A³, and A⁴, X¹ , X², X³, m and n. That is,when a large optical anisotropy value is necessary, it is sufficient toselect compounds having many 1,4-phenylene rings and having single bondas bonding group. When a small optical anisotropy value is necessary, itis sufficient to select compounds having many trans-1,4-cyclohexylenegroups.

For the purpose of the present invention, the term “alkyl group” means astraight chain or branched alkyl group having 1 to 15 carbon atoms, andan alkyl group having 1 to 5 carbon atoms is preferable particularlyfrom the viewpoint of low viscosity. Specifically, methyl group, ethylgroup, propyl group, butyl group, pentyl group, hexyl group, heptylgroup, octyl group, nonyl group, isopropyl group, isobutyl group,isoamyl group, isohexyl group, 2-methylbutyl group, 2-methylpentylgroup, and 3-methylpentyl group are preferable, and racemicmodifications, S isomers, and R isomers are comprehended.

For the purpose of the present invention, the term “alkenyl group” meansa straight chain alkenyl group having 2 to 15 carbon atoms. The alkenylgroup preferably includes 1E-alkenyl, 2Z-alkenyl, 3E-alkenyl, and4-alkenyl, and more specifically, 1-ethenyl, 1E-propenyl, 1E-butenyl,1E-hexenyl, 2-propenyl, 2Z-butenyl, 2Z-pentenyl, 2Z-hexenyl, 3-butenyl,3E-pentenyl, and 3E-hexenyl can be mentioned.

As rings A¹, A², A³, and A⁴, while benzene ring, cyclohexane ring,pyrimidine ring, pyridine ring, pyrazine ring, pyridazine ring, dioxanering, dithian ring, and their halogen substituted ring can be mentioned,cyclohexane ring, benzene ring, and their halogen substituted ring areespecially preferable.

Preferable embodiments of the compounds of the present inventionexpressed by the general formula (1) are compounds expressed by one ofthe following general formulas (1-1) to (1-217):

wherein R¹ and Y¹ have the same meaning as described above.

Any compounds expressed by one of the general formulas (1-1) to (1-11),(1-21) to (1-64), and (1-81) to (1-181) are low in viscosity and exhibita medium extent of dielectric anisotropy. Among them, two rings or threerings compounds expressed by one of the general formulas (1—1) to (1-11)and (1-21) to (1-42) can remarkably lower only viscosity of liquidcrystal compositions without lowering clearing point when added to thecompositions as their component since the compounds are particularly lowin viscosity and excellent in miscibility at low temperatures. Fourrings compounds expressed by one of the general formulas (1-43) to(1-64) and (1-81) to (1-181) can raise only clearing point withoutraising viscosity when added to liquid crystal compositions as theircomponent since the compounds have a wide temperature range of nematicphase and are low in viscosity.

Compounds expressed by one of the general formulas (1-97) to (1-136) and(1-160) to (1-181) have a characteristic: that their optical anisotropyis high, in addition to the characteristic of the four rings compoundsdescribed above. Among them, tolan derivatives expressed by one of thegeneral formulas (1-160) to (1-181) are low in viscosity and have anextremely high optical anisotropy, and thus they exhibit excellentcharacteristics as liquid crystal materials for STN.

Any compounds expressed by one of the general formulas (1-12) to (1-20),(1-65) to (1-70), and (1-182) to (1-217) can increase only dielectricanisotropy in negative numeral without raising viscosity of liquidcrystal compositions when added to the compositions as their componentsince the compounds are extremely low in viscosity and exhibit such acharacteristics that they have a high negative dielectric anisotropy,and thus the compounds can provide liquid crystal compositions whichachieve both low voltage driving and high speed response in the displaydevices of IPS driving or such a vertical orientation mode as disclosedin Laid-open Japanese Patent Publication No. Hei 2-176625.

Further, any derivatives expressed by one of the general formulas (1-1)to (1-217) wherein one or more of R¹ and Y¹ are an alkenyl group exhibitan extremely large elastic constant ratio K33/K11. The derivatives arelow in viscosity and exhibit a high clearing point compared withsaturated compounds having the same skeleton. As described above, thecompounds of the present invention have excellent characteristics, andthus liquid crystal compositions and liquid crystal display deviceshaving improved characteristics can be provided by using the compounds.

Liquid crystal compositions of the present invention are described inmore detail below. Liquid crystal compositions of is the presentinvention preferably comprise at least one compound expressed by thegeneral formula (1) in the ratio of 0.1 to 99.9 % by weight to developexcellent characteristics.

More specifically, liquid crystal compositions provided according to thepresent invention are accomplished by mixing a compound optionallyselected from the group of compounds expressed by one of the generalformulas (2) to (4) depending on the purposes of liquid crystalcompositions in addition to a first component comprising at least onecompound expressed by the general formula (1).

As the compound expressed by one of the general formulas (2) to (4), thefollowing compounds can preferably be mentioned:

wherein R² and y² have the same meaning as described above.

Compounds expressed by one of the general formulas (2) to (4) have apositive dielectric anisotropy value and are remarkably excellent inthermal stability and chemical stability, and thus the compounds areparticularly useful when liquid crystal compositions for TFT displaymode, of which a high reliability represented by a high voltage holdingratio and a large resistivity is required, are produced.

When liquid crystal compositions for TFT display mode are produced,while a compound expressed by one of the general formulas (2) to (4) canoptionally be used in the range of 0.1 to 99.9% by weight based on thetotal amount of liquid crystal composition in addition to a firstcomponent comprising at least one compound expressed by the generalformula (1), the amount of the compound of the general formula (2) to(4) is preferably 10 to 97% by weight and more desirably 40 to 95% byweight.

Also, when liquid crystal compositions for STN display mode or TNdisplay mode are produced, a compound expressed by one of the generalformulas (2) to (4) can be used in addition to the first componentcomprising at least one compound expressed by the general formula (1),but the amount of the compound of the general formula (2) to (4) ispreferably less than 50% by weight in this case.

To the liquid crystal compositions thus obtained comprising a compoundexpressed by the general formula (1) and a compound expressed by one ofthe general formulas (2) to (4), the compound selected from a group ofthe compounds expressed by one of the general formulas (5) to (12) mayfurther be added for the. purpose of adjusting viscosity of the liquidcrystal compositions.

As the compound expressed by the general formula (5) or (6), thefollowing compounds can preferably be mentioned:

wherein R³, R⁴, and Y³ have the same meaning as described above.

Compounds expressed by the general formula (5) or (6) have a largepositive dielectric anisotropy value and thus are used particularly forthe purpose of lowering threshold voltage of liquid crystalcompositions. They are used also for the purpose of adjusting opticalanisotropy value and widening the temperature range of nematic phasesuch as raising clearing point. Further, the compounds are used for thepurpose of improving the steepness of voltage-transmittance curve ofliquid crystal compositions for STN display mode or TN display mode.

When the amount of the compound expressed by the general formula (5) or(6) is increased, threshold voltage of liquid crystal compositionslowers and viscosity increases. Accordingly, it is advantageous to usethe compound in a large quantity so far as the viscosity of liquidcrystal compositions satisfies required characteristics, since thecompositions can be driven at a low voltage. While the compoundexpressed by the general formula (5) or (6) can be used in any amount inthe range of 0.1 to 99.9% by weight when liquid crystal compositions forSTN display mode or TN display mode are produced, the amount ispreferably 10 to 97% by weight and more desirably 40 to 95% by weight.

As the compound used in the present invention and expressed by one ofthe general formula (7) to (9), the following compounds can preferablybe mentioned:

wherein R⁵ and R⁶ have the same meaning as described above.

Compounds expressed by one of the general formulas (7) to (9) are smallin absolute value of dielectric anisotropy and are close to neutral.Compounds expressed by the general formula (7) are used principally forthe purpose of adjusting viscosity and adjusting optical anisotropyvalue of liquid crystal compositions. Compounds expressed by the generalformula (8) or (9) are used for the purpose of widening the temperaturerange of nematic phase such as raising clearing point of liquid crystalcompositions or for the purpose of adjusting the optical anisotropyvalue.

When the amount of the compound expressed by one of the general formulas(7) to (9) to be used is increased, threshold voltage of liquid crystalcompositions rises and their viscosity lowers. Accordingly, it isdesirable to use a large quantity of the compound so far as thethreshold voltage of liquid crystal compositions is satisfied. Amount ofthe compound expressed by one of the general formulas (7) to (9) to beused is 40% by weight or less and more desirably less than 35% by weightwhen liquid crystal compositions for TFT display mode are produced.Further, the amount is 70% by weight or less and more desirably lessthan 60% by weight when liquid crystal compositions for STN display modeor TN display mode are produced.

As the compounds used in the present invention and expressed by one ofthe general formulas (10) to (12), the following compounds canpreferably be mentioned:

wherein R⁷ and R⁸ have the same meaning as described above.

Compounds expressed by one of the general formulas (10) to (12) have anegative dielectric anisotropy value. Accordingly, the compounds cancontrol the elastic constant of liquid crystal compositions, which is afunction of dielectric anisotropy value, by mixing with a compoundhaving a positive dielectric anisotropy value, and thereby the steepnessof voltage-transmittance curve of liquid crystal compositions can becontrolled. Accordingly, the compounds can be used for various drivingmodes.

Compounds expressed by one of the general formulas (10) to (12) canoptionally be used in the range of 0.1 to 99.9% by weight, preferably 10to 97% by weight, and more desirably 10 to 60% by weight when liquidcrystal compositions for TFT display mode, STN display mode, or TNdisplay mode are produced.

Except such specific cases as liquid crystal compositions for OCB(Optically Compensated Birefringence) mode, an optically active compoundis sometimes added to liquid crystal compositions generally for thepurpose of inducing helical structure of liquid crystals to adjustrequired twisting angle and to prevent the reverse twist, and theoptically active compound can be added in the same way even in theliquid crystal compositions of the present invention. While any knownoptically active compounds can be used for such purposes, preferableoptically active compounds can be mentioned as follows:

Usually, one of these optically active compounds is added to the liquidcrystal compositions of the present invention to adjust the pitch of thetwist of liquid crystals. The twist pitch is preferably adjusted in therange of 10 to 200 μm in the case of liquid crystal compositions for TFTdisplay mode or TN display mode. In the case of liquid crystalcompositions for STN display mode, the pitch is preferably adjusted inthe range of 6 to 20 μm. In the case of bistable TN mode, the pitch ispreferably adjusted in the range of 1.5 to 4 μm. Further, two or morekind of optically active compounds may be added for the purpose ofadjusting the dependency of the pitch on temperature.

Liquid crystal compositions of the present invention can be produced bymethods which are known in public by themselves. Generally, a methodwherein various components are dissolved in each other at a hightemperature is adopted.

Liquid crystal compositions of the present invention can be used as onesfor guest-host (GH) mode by adding a dichroic dye such as merocyaninetype, styryl type, azo type, azomethine type, azoxy type, quinophthalonetype, anthraquinone type, or tetrazine type dye. Liquid crystalcompositions of the present invention can also be used as ones for NCAPwhich is prepared by the microencapsulation of a nematic liquid crystal,or for a polymer dispersed liquid crystal display device (PDLCD)represented by polymer network liquid crystal display device (PNLCD)prepared by forming polymers of three-dimensional reticulated structurein a liquid crystal. In addition, the liquid crystal compositions of thepresent invention can be used as ones for electrically controlledbirefringence (ECB) mode or dynamic scattering (DS) mode.

As nematic liquid crystal compositions comprising the liquid crystallinecompound of the present invention, the following composition examplescan be mentioned. In the composition examples, compounds are designatedby using symbols according to the definitions shown in Table 1 below.

Further, in the case where hydrogen atoms of trans-1,4-cyclohexylene arereplaced by deuterium atom at positions Q¹, Q², and Q³, it is designatedas symbol H [1D, 2D, 3D]. In the case where the hydrogen atom isreplaced at positions Q⁵, Q⁶, and Q⁷, it is designated as symbol H [5D,6D, 7D]. Thus, the position where deuterium atom substituted isindicated by the number in the parenthesis.

TABLE 1 Method for designating compounds by using symbols R—(A₁)—Z₁— . .. —Z_(n)—(A_(n))—X 1) Left side terminal group R— Symbol C_(n)H_(2n+1)—n- C_(n)H_(2n+1)O— nO- C_(n)H_(2n+1)OC_(m)H_(2m)— nOm- CH₂═CH— V-CH₂═CHC_(n)H_(2n)— Vn- C_(n)H_(2n+1)CH═CHC_(m)H_(2m)— nVm-C_(n)H_(2n+1)CH═CHC_(m)H_(2m)CH═CHC_(k)H_(2k)— nVmVk- 2) Ring structure—(A₁)—, —(A_(n))— Symbol

B

B(F)

B(2F, 3F)

B(F, F)

H

Py

D

Ch 3) Bonding group —Z₁—, —Z_(n)— Symbol —C₂H₄— 2 —C₄H₈— 4 —COO— E —C≡C—T —CH═CH— V —CF₂O— CF2O —OCF₂— OCF2 4) Right side terminal group —XSymbol —F —F —Cl —CL —CN —C —CF₃ —CF3 —OCF₃ —OCF3 —OCF₂H —OCF2H—C_(n)H_(2n+1) -n —OC_(n)H_(2n+1) —On —COOCH₃ —EMe —C_(n)H_(2n)CH═CH₂-nV —C_(m)H_(2m)CH═CHC_(n)H_(2n+1) -mVn —C_(m)H_(2m)CH═CHC_(n)H_(2n)F-mVnF —CH═CF₂ —VFF —C_(n)H_(2n)CH═CF₂ -nVFF —C≡C—CN —TC 5) Example ofdesignation Example 1 3-H2B(F, F)B(F)—F

Example 2 3-HB(F)TB-2

Example 3 1V2-BEB(F, F)—C

Composition Example 1

3-H2B(F)EB(2F, 3F)-O2 15.0% 1V2-BEB(F, F)-C 5.0% 3-HB-C 25.0% 2-BTB-111.0% 3-HH-4 10.0% 3-HHB-1 10.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-44.0% 3-HB(F)TB-2 6.0% 3-HB(F)TB-3 6.0% CM33 0.8 part

Composition Example 2

5-HVHEB(2F, 3F)-O2 7.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 15.0%3-H[1D, 2D, 3D]-C 9.0% 3-HB(F)-C 5.0% 2-BTB-1 2.0% 3-HH-4 6.0% 3-HH-VFF6.0% 2-H[1D, 2D, 3D]HB-C 3.0% 3-HHB-C 3.0% 3-HB(F)TB-2 6.0% 3-H2BTB-25.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0%

Composition Example 3

3-H2B(F)EB(2F, 3F)-O2 10.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 15.0%4O1-BEB(F)-C 13.0% 5O1-BEB(F)-C 11.0% 2-HHB(F)-C 15.0% 3-HHB(F)-C 15.0%3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-O1 4.0%

Composition Example 4

3-H2B(F)EB(2F, 3F)-O2 6.0% 5-HVHEB(2F, 3F)-O2 6.0% 5-PyB-F 4.0%3-PyB(F)-F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0% 3-PYB-22.0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 3-PyBB-F6.0% 4-PyBB-F 6.0% 5-PyBB-F 6.0% 3-HHB-1 5.0% 2-H2BTB-2 4.0% 2-H2BTB-34.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0%

Composition Example 5

5-HVHEB(2F, 3F)-O2 7.0% 5-HBCF2OB(2F, 3F)-O2 13.0% 3-HB-C 18.0% 7-HB-C3.0% 1O1-HB-C 10.0% 3-HB(F)-C 10.0% 2-PyB-2 2.0% 3-PYB-2 2.0% 4-PyB-22.0% 1O1-HH-3 4.0% 2-BTB-O1 5.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-H2BTB-23.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0%

Composition Example 6

3-H2B(F)EB(2F, 3F)-O2 4.0% 5-HVHEB(2F, 3F)-O2 4.0% 5-HBCF2OB(2F, 3F)-O24.0% 5-BEB(F)-C 5.0% V-HB-C 11.0% 5-PyB-C 6.0% 4-BB-3 11.0% 3-HH-2V 6.0%5-HH-V 11.0% V-HHB-1 7.0% V2-HHB-1 11.0% 3-HHB-1 5.0% 1V2-HBB-2 10.0%3-HHEBH-3 5.0%

Composition Example 7

3-H2B(F)EB(2F, 3F)-O2 7.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.&%5O1-BEB(F)-C 4.0% 1V2-BEB(F, F)-C 16.0% 3-HB-O2 10.0% 3-HH-4 3.0%3-HHB-F 3.0% 3-HHB-1 3.0% 3-HHB-O1 2.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0%5-HHEB-F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-25.0%

Composition Example 8

5-HBCF2OB(2F, 3F)-O2 10.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 4-BEB-C 6.0%3-HB-C 28.0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0%3-HHB-1 2.0% 3-HHB-O1 4.0%

Composition Example 9

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O25.0% 2-BEB-C 10.0% 5-BB-C 12.0% 7-BB-C 7.0% 1-BTB-3 7.0% 2-BTB-1 10.0%1O-BEB-2 10.0% 1O-BEB-5 10.0% 2-HHB-1 4.0% 3-HHB-F 4.0% 3-HHB-1 7.0%3-HHB-O1 4.0%

Composition Example 10

5-HVHEB(2F, 3F)-O2 7.0% 5-HBCF2OB(2F, 3F)-O2 8.0% 1V2-BEB(F, F)-C 8.0%3-HB-C 10.0% V2V-HB-C 14.0% V2V-HH-3 16.0% 3-HB-O2 4.0% 3-HHB-1 10.0%3-HHB-3 3.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-34.0% 3-H2BTB-4 4.0%

Composition Example 11

5-HVHEB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O2 6.0% 5-BTB(F)TB-3 10.0%V2-HB-TC 10.0% 3-HB-TC 10.0% 3-HB-C 10.0% 5-HB-C 7.0% 5-BB-C 3.0%2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4 5.0% 3-HHB-1 10.0% 3-H2BTB-2 3.0%3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0%

Composition Example 12

5-HVHEB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O2 4.0% 1V2-BEB(F, F)-C 6.0%3-HB-C 18.0% 2-BTB-1 10.0% 5-HH-VFF 30.0% 1-BHH-VFF 8.0% 1-BHH-2VFF 4.0%3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0%

Composition Example 13

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O2 10.0% 5-HBCF2OB(2F, 3F)-O210.0% 2-HB-C 5.0% 3-HB-C 12.0% 3-HB-O2 12.0% 2-BTB-1 3.0% 3-HHB-1 3.0%3-HHB-F 4.0% 3-HHB-O1 2.0% 3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB(F)-F 7.0%3-HHB(F)-F 7.0% 5-HHB(F)-F 7.0% 3-HHB(F, F)-F 5.0%

Composition Example 14

5-HBCF2OB(2F, 3F)-O2 10.0% 2-HHB(F)-F 17.0% 3-HHB(F)-F 17.0% 5-HHB(F)-F16.0% 2-H2HB(F)-F 10.0% 3-H2HB(F)-F 5.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0%5-HBB(F)-F 13.0% CN 0.3 part

Composition Example 15

5-HVHEB(2F, 3F)-O2 8.0% 5-HBCF2OB(2F, 3F)-O2 5.0% 7-HB(F)-F 5.0%5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH [5D, 6D, 7D]-4 3.0%2-HHB(F)-F 10.0% 3-HHB(F)-F 5.0% 5-HH [5D, 6D, 7D] B(F)-F 10.0%3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0%2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-O1 5.0% 3-HHB-3 4.0%

Composition Example 16

3-H2B(F)EB(2F, 3F)-O2 3.0% 5-HVHEB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O24.0% 7-HB(F, F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0%2-HBB(F)-F 9.0% 3-HBB(F)-F 9.0% 5-HBB(F)-F 16.0% 2-HBB-F 4.0% 3-HBB-F4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F 5.0% 5-HBB(F, F)-F 10.0%

Composition Example 17

5-HBCF2OB(2F, 3F)-O2 15.0% 7-HB(F, F)-F 3.0% 3-H2HB(F, F)-F 12.0%4-H2HB(F, F)-F 10.0% 5-H2HB(F, F)-F 10.0% 3-HHB(F, F)F 5.0% 4-HHB(F,F)-F 5.0% 3-HH2B(F, F)-F 15.0% 3-HBB(F, F)-F 12.0% 5-HBB(F, F)-F 7.0%3-HBCF2OB(F, F)-F 6.0%

Composition Example 18

3-H2B(F)EB(2F, 3F)-O2 10.0% 7-HB(F, F)-F 5.0% 3-H2HB(F, F)-F 12.0%3-HHB(F, F)-F 10.0% 4-HHB(F, F)-F 5.0% 3-HBB(F, F)-F 10.0% 3-HHEB(F,F)-F 10.0% 4-HHEB(F, F)-F 3.0% 5-HHEB(F, F)-F 3.0% 2-HBEB(F, F) 3.0%3-HBEB(F, F) 5.0% 5-HBEB(F, F) 3.0% 3-HDB(F, F) 15.0% 3-HHBB(F, F)-F6.0%

Composition Example 19

5-HBCF2OB(2F, 3F)-O2 10.0% 3-BCF2OB(2F, 3F)-O2 10.0% 3-HHB(F, F)-F 9.0%3-H2HB(F, F)-F 8.0% 4-H2HB(F, F)-F 8.0% 5-H2HB(F, F)-F 8.0% 3-HBB(F,F)-F 11.0% 5-HBB(F, F)-F 10.0% 3-H2BB(F, F)-F 10.0% 5-HHBB(F, F)-F 3.0%5-HHEBB-F 2.0% 3-HH2BB(F, F)-F 3.0% 1O1-HBBH-4 4.0% 1O1-HBBH-5 4.0%

Composition Example 20

5-HBCF2OB(2F, 3F)-O2 4.0% 5-B2BCF2OB(2F, 3F)O2 4.0% 3-BCF2OB(2F, 3F)-O24.0% 5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F 7.0% 2-HHB-OCF3 7.0% 3-HHB-OCF37.0% 4-HHB-OCF3 7.0% 5-HHB-OCF3 5.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0%3-HHB(F, F)-OCF3 5.0% 3-HEB(F)-F 8.0% 3-HH2B(F)-F 3.0% 3-HB(F)BH-3 3.0%5-HBBH-3 3.0% 3-HHB(F, F)-OCF2H 4.0%

Composition Example 21

3-H2B(F)EB(2F, 3F)-O2 15.0% 3-HEB-O4 23.0% 4-HEB-O2 18.0% 5-HEB-O1 18.0%3-HEB-O2 14.0% 5-HEB-O2 12.0%

Composition Example 22

5-HBCF2OB(2F, 3F)-O2 15.0% 5-HVHEB(2F, 3F)-O2 5.0% 3-HB-O2 10.0% 3-HB-O410.0% 3-HEB-O4 16.0% 4-HEB-O2 13.0% 5-HEB-O1 13.0% 3-HEB-O2 10.0%5-HEB-O2 8.0%

Composition Example 23

5-HBCF2OB(2F, 3F)-O2 15.0% 3-HB-O2 15.0% 3-HB-O4 10.0% 3-HEB-O4 10.0%4-HEB-O2 7.0% 5-HEB-O1 7.0% 3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HB(2F, 3F)-O27.0% 5-HHB(2F, 3F)-O2 5.0% 5-HBB(2F, 3F)-2 5.0% 5-HBB(2F, 3F)-O2 4.0%5-BB(2F, 3F)B-3 4.0%

Composition Example 24

3-BCF2OB(2F, 3F)-O2 20.0% 3-H2B(F)EB(2F, 3F)-O2 15.0% 5-HBCF2OB(2F,3F)-O2 15.0% 3-HB(2F, 3F)-O2 20.0% 5-HHB(2F, 3F)-O2 10.0% 5-HHB(2F,3F)-1O1 5.0% 5-HBB(2F, 3F)-2 10.0% 5-HBB(2F, 3F)-1O1 5.0%

Composition Example 25

3-BCF2OB(2F, 3F)-O2 10.0% 3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O25.0% 5-BBCF2OB(2F, 3F)-O2 5.0% 3-DB-C 10.0% 4-DB-C 10.0% 2-BEB-C 12.0%3-BEB-C 4.0% 3-PyB(F)-F 6.0% 3-HEB-O2 3.0% 5-HEB-O2 4.0% 5-HEB-5 5.0%4-HEB-5 5.0% 1O-BEB-2 4.0% 3-HHB-1 3.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0%5-HBEBB-C 3.0%

Composition Example 26

3-H2HCF2OB(2F, 3F)-O2 10.0% 3-HVBCF2OB(2F, 3F)-O2 5.0% 5-H2BCF2OB(2F,3F)-O2 5.0% 3-HHBCF2OB(2F, 3F)-O2 3.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C12.0% 5O1-BEB(F)-C 4.0% 1V2-BEB(F, F)-C 10.0% 3-HH-EMe 5.0% 3-HB-O218.0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0%2O1-HBEB(F)-C 2.0% 3-HB(F)EB(F)-C 2.0% 3-HBEB(F, F)-C 2.0% 3-HHB-F 2.0%3-HHB-3 1.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0%

Composition Example 27

3-B(F)EB(2F,3F)-O2 5.0% 3-BCF2OB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O25.0% 5-H2BCF2OB(2F, 3F)-O2 10.0% 5-B2BCF2OB(2F, 3F)-O2 15.0% 5-HB-CL4.0% 7-HB-CL 4.0% 1O1-HH-5 3.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 4-HHB-CL4.0% 5-HHB-CL 8.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0% 5-H2BB(F, F)-F9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0%

Composition Example 28

3-B(F) EB(2F, 3F)-O2 5.0% 5-HVBEB(2F, 3F)-O3 5.0% 5-H2B(F)EB(2F, 3F)-O25.0% 5-H4HB(F, F)-F 7.0% 5-H4HB-OCF3 15.0% 3-H4HB(F, F)-CF3 3.0% 3-HB-CL6.0% 5-HB-CL 4.0% 2-H2BB(F)-F 5.0% 3-H2BB(F)-F 10.0% 5-HVHB(F, F)-F 5.0%3-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0% V-HHB(F)-F 5.0% 3-HHB(F)-F 5.0%5-HHEB-OCF3 2.0% 3-HBEB(F, F)-F 5.0% 5-HH-V2F 3.0%

Composition Example 29

5-B(F)CF2OB(2F, 3F)-O1 5.0% 3-H2HB(F)EB(2F, 3F)-O2 3.0% 3-HH2BCF2OB(2F,3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O2 5.0% 2-HHB(F)-F 2.0% 3-HHB(F)-F 2.0%5-HHB(F)-F 2.0% 2-HBB(F)-F 6.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F 10.0%2-H2BB(F)-F 9.0% 3-H2BB(F)-F 9.0% 3-HBB(F, F)-F 15.0% 5-HBB(F, F)-F19.0% 1O1-HBBH-4 4.0%

Composition Example 30

5-B(F)CF2OB(2F, 3F)-O1 5.0% 5-HBCF2OB(2F, 3F)-O2 5.0% 5-HB-CL 12.0%3-HH-4 2.0% 3-HB-O2 20.0% 3-H2HB(F, F)-F 5.0% 3-HHB(F, F)-F 8.0%3-HBB(F, F)-F 6.0% 2-HHB(F)-F 5.0% 3-HHB(F)-F 5.0% 5-HHB(F)-F 5.0%2-H2HB(F)-F 2.0% 3-H2HB(F)-F 1.0% 5-H2HB(F)-F 2.0% 3-HHBB(F, F)-F 4.0%3-HBCF2OB-OCF3 4.0% 5-HBCF2OB(F, F)-OCF3 4.0% 3-HHB-1 3.0% 3-HHB-O1 2.0%

Composition Example 31

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 7.0% 7-HB(F)-F 14.0% 2-HHB(F)-F 11.0%3-HHB(F)-F 11.0% 5-HHB(F)-F 11.0% 2-H2HB(F)-F 5.3% 3-H2HB(F)-F 2.6%5-H2HB(F)-F 5.3% 2-HBB(F)-F 6.2% 2-HBB(F)-F 6.2% 2-HBB(F)-F 12.4%

Composition Example 32

5-HBCF2OBH-3 7.0% 3-H2BCF2OBH-3 7.0% 3-H2BCF2OBH-5 6.0% 7-HB(F, F)-F4.0% 3-HHB(F, F)-F 6.0% 3-H2HB(F, F)-F 5.0% 3-HBB(F, F)-F 12.0% 5-HBB(F,F)-F 12.0% 3-H2BB(F, F)-F 5.0% 4-H2BB(F, F)-F 5.0% 5-H2BB(F, F)-F 5.0%3-HBEB(F, F)-F 2.0% 4-HBEB(F, F)-F 2.0% 5-HBEB(F, F)-F 2.0% 3-HHEB(F,F)-F 12.0% 4-HHEB(F, F)-F 4.0% 5-HHEB(F, F)-F 4.0%

Composition Example 33

3-HBCF2OB-3 5.0% 3-BCF2OBH-5 5.0% 3-H2HB(F, F)-F 9.0% 5-H2HB(F, F)-F8.0% 3-HHB(F, F)-F 9.0% 4-HHB(F, F)-F 5.0% 3-HH2B(F, F)F 11.0% 5-HH2B(F,F)-F 7.0% 3-HBB(F, F)-F 14.0% 5-HBB(F, F)-F 14.0% 3-HHEB(F, F)-F 9.0%3-HHBB(F, F)-F 2.0% 3-HH2BB(F, F)-F 2.0%

Composition Example 34

3-HBCF2OBH-3 6.0% 3-HBCF2OBH-5 4.0% 3-H2BCF2OBH-2 5.0% 7-HB(F, F)-F 4.0%7-HB(F)-F 6.0% 2-HHB(F)-F 11.5% 3-HHB(F)-F 11.5% 5-HHB(F)-F 11.5%2-H2HB(F)-F 3.0% 3-H2HB(F)-F 1.5% 5-H2HB(F)-F 3.0% 3-H2HB(F, F)-F 5.0%4-H2HB(F, F)-F 4.0% 5-H2HB(F, F)-F 4.0% 3-HHB(F, F)-F 7.0% 3-HH2B(F,F)-F 7.0% 5-HH2B(F, F)-F 6.0%

Composition Example 35

3-HB(F)CF26B-3 8.0% 3-HB(F, F)CF2OB-5 5.0% 2-HBCF2OBH-2 7.0% 7-HB(F,F)-F 4.0% 2-HHB(F)-F 11.1% 3-HHB(F)-F 11.2% 5-HHB(F)-F 11.2% 2-H2HB(F)-F3.0% 3-H2HB(F)-F 1.5% 5-H2HB(F)-F 3.0% 3-H2HB(F, F)-F 5.0% 4-H2HB(F,F)-F 3.0% 5-H2HB(F, F)-F 3.0% 3-HHB(F, F)-F 8.0% 4-HHB(F, F)-F 4.0%3-HH2B(F, F)-F 6.0% 5-HH2B(F, F)-F 6.0%

Composition Example 36

3-HBCF2OB-5 7.0% 3-HB(F)CF2OBH-3 5.0% 3-HB(F)CF2OBTB-3 3.0% 3-HB-Cl 7.0%7-HB(F, F)-F 10.0% 2-HBB(F)-F 6.5% 3-HBB(F)-F 6.5% 5-HBB(F)-F 13.0%2-HHB-CL 5.0% 4-HHB-CL 8.0% 5-HHB-CL 5.0% 3-HBB(F, F)-F 10.0% 5-HBB(F,F)-F 8.0% 3-HB(F)VB-2 3.0% 3-HB(F)VB-3 3.0%

Composition Example 37

3-BCF2OBH-V 5.0% 5-HB(F, F)CF2OBH-3 3.0% 2-BTBCF2OBH-2 3.0%3-BTB(F)CF2OBH-3 3.0% 5-HB-CL 5.0% 7-HB-CL 6.0% 2-HBB(F)-F 7.0%3-HBB(F)-F 7.0% 5-HBB(F)-F 14.0% 2-HHB-CL 5.0% 4-HHB-CL 5.0% 5-HHB-CL4.0% 3-HBB(F, F)-F 16.0% 5-HBB(F, F)-F 14.0% 3-HB(F)TB-2 3.0%

Composition Example 38

5-HBCF2OBH-3 6.0% 3-HBCF2OBH-3 6.0% 5-HBCF2OBTB-3 3.0% 2-HHB(F)-F 8.0%3-HHB(F)-F 8.0% 5-HHB(F)-F 8.0% 3-HHB(F, F)-F 6.0% 5-HHB(F, F)-F 5.0%3-H2HB(F, F)-F 7.0% 4-H2HB(F, F)-F 7.0% 5-H2HB(F, F)-F 7.0% 3-HH2B(F,F)-F 12.0% 5-HH2B(F, F)-F 8.0% 2-HBB-F 3.0% 3-HBB-F 3.0% 3-HHB-1 3.0%

Composition Example 39

5-HBCF2OB-3 5.0% 2-HB(F)CF2OB-3 5.0% 3-HB(F)CF2OB-3 5.0% 7-HB(F)-F 4.0%2-HHB(F)-F 13.0% 3-HHB(F)-F 13.0% 5-HHB(F)-F 13.0% 2-H2HB(F)-F 6.0%3-H2HB(F)-F 3.0% 5-H2HB(F)-F 6.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0%5-HBB(F)-F 6.0% 3-HBB-F 2.0% 3-HHB-F 3.0% 3-HB-O2 5.0% 3-HHB-1 3.0%1O1-HBBH-3 2.0%

Composition Example 40

5-HBCF2OB-3 8.0% 3-BCF2OBH-V 8.0% 2-BCF2OBH-2V 8.0% 3-HB(F)CF2OBH-3 6.0%7-HB(F, F)-F 5.0% 5-H2B(F)-F 5.0% 2-HHB(F)-F 4.0% 3-HHB(F)-F 4.0%5-HHB(F)-F 4.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 16.0% 2-HBB-F4.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0%

Composition Example 41

3-HB(F, F)CF2OB-1 4.0% 3-HB(F, F)CF2OBH-3 4.0% 2-BTB(F, F)CF2OBH-2 2.0%2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HHB(F)-F 10.0% 2-HBB(F)-F 5.0%3-HBB(F)-F 5.0% 5-HBB(F)-F 10.0% 3-HHB(F, F)-F 7.0% 5-HHB(F, F)-F 4.0%3-HH2B(F, F)-F 8.0% 5-HH2B(F, F)-F 8.0% 5-H2HB(F, F)-F 5.0% 5-HHEBB-F2.0% 3-HB-O2 4.0% 3-HHB-O1 2.0%

Composition Example 42

5-HBCF2OB-3 5.0% 3-BCF2OBH-V 4.0% 5-HBCF2OBH-3 5.0% 3-H2BCF2OBH-3 5.0%2-HHB(F)-F 4.0% 3-HHB(F)-F 4.0% 5-HHB(F)-F 4.0% 2-HBB(F)-F 4.0%3-HBB(F)-F 4.0% 5-HBB(F)-F 8.0% 4-H2BB(F)-F 6.0% 5-H2BB(F)-F 6.0%3-H2BB(F, F)-F 4.0% 4-H2BB(F, F)-F 5.0% 5-H2BB(F, F)-F 4.0% 3-HBB(F,F)-F 12.0% 5-HBB(F, F)-F 8.0% 3-HH2B(F, F)-F 4.0% 5-HH2B(F, F)-F 4.0%

Composition Example 43

5-HBCF2OB-3 6.0% 3-BCF2OBH-V 4.0% 5-HBCF2OBH-3 5.0% 3O1-BEB(F)-C 12.0%V2-HB-C 10.0% 3-HB-O2 4.0% 2-BTB-O1 5.0% 3-BTB-O1 5.0% 4-BTB-O1 5.0%4-BTB-O2 5.0% 5-BTB-O1 5.0% 3-HHB-O1 3.0% 3-H2BTB-2 2.0% 3-H2BTB-3 3.0%3-H2BTB-4 3.0% 3-HB(F)TB-2 3.0% 3-HB(F)TB-3 3.0% 3-HB(F)TB-4 5.0%2-PyBH-3 4.0% 3-PyBH-3 4.0% 3-PyBB-2 4.0%

Composition Example 44

5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 3-H2BCF2OBH-5 5.0% V2-HB-C 9.0%1V2-HB-C 9.0% 3-HB-C 4.0% 1O1-HB-C 8.0% 2O1-HB-C 4.0% 2-HHB-C 5.0%3-HHB-C 5.0% 3-HH-4 8.0% 1O1-HH-5 5.0% 2-BTB-O1 8.0% 3-HHB-1 4.0%3-HHB-3 4.0%

Composition Example 45

3-BCF2OBH-V 3.0% 5-BCF2OBH-2V 4.0% 3-BCF2OBH-2V1 4.0% 3-H2BCF2OBH-5 4.0%1V2-BEB(F, F)-C 12.0% 3O1-BEB(F)-C 12.0% 2-HB-C 12.0% 3-HB-C 19.0%2-HHB-C 4.0% 3-HHB-C 5.0% 4-HHB-C 4.0% 5-HHB-C 4.0% 3-HB-O2 5.0%3-H2BTB-3 4.0% 3-H2BTB-4 4.0%

Composition Example 46

5-HBCF2OB-3 10.0% 3-HB(F)CF2OB-3 10.0% 2-HB(F)CF2OBH-V 4.0%3-HB(F)CF2OBH-V1 3.0% 3-BTBCF2OBH-3 3.0% V2-HB-C 12.0% 1V2-HB-C 11.0%1V2-BEB(F, F)-C 11.0% 2-BTB-1 5.0% 4-BTB-O2 5.0% 5-BTB-O1 5.0% 3-HH-EMe4.0% 2-H2BTB-3 4.0% 2-H2BTB-2 4.0% 3-HB(F)TB-2 3.0% 3 HB(F)TB-3 3.0% 3HB(F)TB-4 3.0%

Composition Example 47

2-HBCF2OBH-2 6.0% 3-HBCF2OBH-3 6.0% 3-HB(F, F)CF2OBH-V 3.0% 3-HB(F,F)CF2OBH-2V1 3.0% 2O1-BEB(F)-C 4.0% 3O1-BEB(F)-C 12.0% 5O1-BEB(F)-C 4.0%1V2-BEB(F, F)-C 15.0% 3-HHEB-F 5.0% 5-HHEB-F 5.0% 3-HBEB-F 6.0% 3-HHB-F3.0% 3-HB-O2 10.0% 3-HH-4 5.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-HB(F)VB-25.0%

Composition Example 48

3-HBCF2OB-3 7.0% 2-HB(F)CF2OBH-2V 3.0% 3-HB(F)CF2OBH-2V1 3.0% 3-HB(F,F)CF2OBTB-3 3.0% 2-HB(F)-C 15.0% 2-HEB-F 2.4% 3-HEB-F 2.3% 4-HEB-F 2.3%3-HHEB-F 4.0% 5-HHEB-F 4.0% 2-HHB(F)-C 12.0% 3-HHB(F)-C 12.0% 2-HHB(F)-F10.0% 3-HHB(F)-F 10.0% 5-HHB(F)-F 10.0%

Composition Example 49

3-BCF2OBH-3 7.0% 2-BCF2OBH-V 7.0% 3-HB(F, F)CF2OBH-V1 3.0% 3-HB(F,F)CF2OBH-2V 3.0% 3-HB(F)-C 3.0% 3-HB-C 21.0% 3-HHB-C 5.0% 5-PyB-F 10.0%3-HB-O2 4.0% 2-BTB-1 6.0% 3-HH-4 6.0% 3-HH-5 6.0% 3-HHB-1 5.0% 3-HHB-37.0% 3-HHB-O1 3.0% 3-HEBEB-2 2.0% 3-HEBEB-F 2.0%

Composition Example 50

3-HBCF2OBH-3 8.0% 3-HBCF2OBH-5 8.0% 3-HB(F)CF2OBTB-3 4.0% 2-BB-C 8.0%4-BB-C 6.0% 2-HB-C 10.0% 3-HB-C 13.0% 3-HHB-F 5.0% 2-HHB-C 4.0% 3-HHB-C6.0% 5-PyB-F 6.0% 3-PyBB-F 6.0% 2-HHB-1 6.0% 3-HHB-3 5.0% 3-HHB-O1 5.0%

Composition Example 51

5-HBCF2OB-3 8.0% 3-BCF2OBH-V 8.0% 3-HB(F)CF2OBH-3 6.0% 5-BB-C 8.0%3-HHB-F 4.0% 3-HB-O2 12.0% 3-HB-O4 10.0% 3-PyB-4 2.5% 4-PyB-4 2.5%6-PyB-4 2.5% 3-PyB-5 2.5% 4-PyB-5 2.5% 6-PyB-5 2.5% 6-PyB-O5 3.0%6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB-O8 3.0% 2-HHB-1 4.0% 3-HHB-1 8.0%3-HHB-O1 5.0%

Composition Example 52

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 3-DB-C 10.0%4-DB-C 12.0% 5-DB-C 8.0% 2-BEB-C 10.0% 5-PyB(F)-F 10.0% 2-PyB-2 1.4%3-PyB-2 1.3% 4-PyB-2 1.3% 3-HEB-O4 2.2% 4-HEB-O2 1.6% 3-HEB-O2 1.3%1O-BEB-2 1.1% 5-HEB-1 1.6% 4-HEB-4 2.2% 3-HHB-3 6.0% 3-HHB-O1 4.0%2-PyBH-3 6.0%

Composition Example 53

2-HBCF2OB-2 6.0% 3-HBCF2OB-3 4.0% 5-HBCF2OBH-3 6.0% 3-DB-C 10.0% 4-DB-C10.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C3.0% 3-PyB(F)-F 6.0% 3-HEB-O4 8.3% 4-HEB-O2 6.2% 5-HEB-O1 6.2% 3-HEB-O25.2% 5-HEB-O2 4.1% 3-HHB-1 3.0%

Composition Example 54

3-H2BCF2OBH-3 5.0% 3-H2BCF2OBH-5 5.0% 5-HB-F 4.0% 7-HB-F 7.0% 3-HHB-OCF310.0% 5-HHB-OCF3 8.0% 3-H2HB-OCF3 6.0% 5-H2HB-OCF3 5.0% 2-HHB(F)-F 5.0%3-HHB(F)-F 5.0% 5-HHB(F)-F 5.0% 3-H2HB(F, F)-F 6.0% 4-H2HB(F, F)-F 5.0%5-H2HB(F, F)-F 5.0% 3-HHB(F, F)-F 8.0% 3-HH2B(F, F)-F 6.0%

Composition Example 55

5-HBCF2OB-3 8.0% 5-HBCF2OBH-3 6.0% 3-H2BCF2OBH-3 6.0% 7-HB-F 5.0%3-HB-O2 4.0% 3-HHB-OCF3 10.0% 5-HHB-OCF3 5.0% 3-H2HB-OCF3 5.0%5-H2HB-OCF3 5.0% 2-HHB(F)-F 7.0% 3-HHB(F)-F 7.0% 5-HHB(F)-F 7.0%2-H2HB(F)-F 4.0% 3-H2HB(F)-F 2.0% 5-H2HB(F)-F 4.0% 2-HBB(F)-F 3.0%3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0% 3-HHB-1 3.0%

Composition Example 56

3-BCF2OBH-V 6.0% 5-HBCF2OBH-3 4.0% V2-HB-C 9.0% 1V2-HB-C 9.0% 3-HB-C14.0% 1O1-HB-C 8.0% 2O1-HB-C 4.0% 2-HHB-C 5.0% 3-HHB-C 5.0% V2-HH-310.0% 1O1-HH-5 4.0% 2-BTB-O1 8.0% V-HHB-1 5.0% V-HBB-2 5.0% 1V2-HBB-24.0%

Composition Example 57

3-BCF2OBH-V 6.0% 3-H2BCF2OBH-3 7.0% 3-H2BCF2OBH-5 7.0% 2O1-BEB(F)-C 4.0%3O1-BEB(F)-C 10.0% 5O1-BEB(F)-C 4.0% V-HB-C 10.0% 1V-HB-C 10.0% 3-HB-C8.0% 2-HHB-C 4.0% 3-HHB-C 4.0% 4-HHB-C 4.0% 5-HHB-C 4.0% 3-HB-O2 5.0%V-HHB-1 5.0% V-HBB-2 4.0% 3-H2BTB-2 4.0%

Composition Example 58

3-BCF2OBH-3 6.0% 5-HB(F, F)CF2OB-3 4.0% 3-HB(F)CF2OBH-3 5.0% 5-HB-F 6.0%6-HB-F 4.0% 7-HB-F 7.0% 5-HB-3 3.0% 3-HB-O1 3.0% 2-HHB-OCF3 5.0%3-HHB-OCF3 5.0% 4-HHB-OCF3 5.0% 5-HHB-OCF3 7.0% 3-HH2B-OCF3 2.0%5-HH2B-OCF3 3.0% 3-HH2B-F 3.0% 5-HH2B-F 3.0% 3-HBB(F)-F 6.0% 5-HBB(F)-F5.0% 3-HH2B(F)-F 7.0% 5-HH2B(F)-F 9.0% 5-HB(F)BH-3 2.0%

Composition Example 59

3HB(F, F)CF2OBH-3 4.0% 2-BTB(F, F)CF2OBH-2 4.0% 2-HBCF2OBTB-2 8.0%5-HB-F 7.0% 3-HH-O1 4.0% 3-HH-O3 4.0% 5-HH-O1 3.0% 3-HHB-OCHF2 5.0%5-HHB-OCHF2 5.0% 3-HHB(F, F)-OCHF2 8.0% 5-HHB(F, F)-OCHF2 8.0%2-HHB-OCHF3 5.0% 3-HHB-OCHF3 5.0% 4-HHB-OCHF3 5.0% 5-HHB-OCHF3 5.0%3-HH2B(F)-F 7.0% 5-HH2B(F)-F 8.0% 3-HHEB(F)-F 5.0%

Composition Example 60

2-BCF2OBH-2V 8.0% 3-HB(F)CF2OBH-V 6.0% 2-HB(F)CF2OBH-2V 6.0% V-HB-C10.0% 1V-HB-C 5.0% 3-BB-C 5.0% 5-BB-C 5.0% 2-HB)F)-C 4.0% 4-BB-3 3.0%3-H2B-O2 3.0% 5-H2B-O2 6.0% 3-BEB-C 5.0% 5-HEB-O1 6.0% 5-HEB-O3 6.0%5-BBB-C 3.0% 4-BPyB-C 4.0% 4-BPyB-5 4.0% 5-HB2B-4 3.0% 5-HBB2B-3 2.0%1V-HH-1O1 3.0% 1V2-HBB-3 3.0%

Composition Example 61

3-BCF2OBH-2V1 6.0% 3-HB(F, F)CF2OBH-3 3.0% 2-BTB(F)CF2OBH-2 6.0%4-HEB(F)-F 8.0% 5-HEB(F)-F 8.0% 2-BEB(F)-C 5.0% 3-BEB(F)-C 5.0%4-BEB(F)-C 6.0% 5-BEB(F)-C 6.0% 1O3-HB(F)-C 6.0% 3-HHEB(F)-F 5.0%5-HHEB(F)-F 5.0% 2-HBEB(F)-C 5.0% 3-HBEB(F)-C 5.0% 4-HBEB(F)-C 5.0%5-HBEB(F)-C 5.0% 3-HBTB-2 5.0% V2-HH-3 3.0% V2-HHB-1 3.0%

Liquid crystalline compounds of the present invention expressed by thegeneral formula (1) can readily produced by ordinary procedures inorganic synthetic chemistry. For instance, the compounds can easily beproduced by selecting proper procedures described in Organic Synthesis,Organic Reactions, Jikken Kagaku Kouza (Course of Chemical Experiment),or others and using them in combination.

For instance, compounds (1-A) expressed by the general formula (1)wherein m is 1, n is 0, and X² is —COO— can preferably be produced bythe following method. That is, the compounds (1-A) can be produced byreacting carboxylic acid derivatives (13) with alcohol or phenolderivatives (14) in a solvent such as dichloromethane and chloroform inthe presence of a dehydrating agent such as dicyclohexylcarbodiimide(DCC), and 4-dimethylaminopyridine (DMAP) (B. Neises et al., OrganicSynthesis, 63, 183 (1985)).

wherein R¹, X¹, Y¹ , and rings A¹, A², and A⁴ have the same meaning asdescribed above.

Compounds (1-B) expressed by the general formula (1) wherein m is 1, nis 0, and X² is —CF₂O— can preferably be produced by the followingmethod. That is, halides (15) are converted into Grignard reagents orlithiated compounds by using magnesium and lithium reagent, and then thereagents or lithiated compounds are reacted with carbon disulfide toproduce dithiocarboxylic acid derivatives (16). Subsequently, thederivatives (16) are reacted with thionyl chloride to convert intothioncarboxylic acid chloride, reacted with an alcohol or phenol toproduce thion-O-ester derivatives (17), and then the derivatives (17) isreacted with diethylaminosulfur trifluoride (hereinafter abbreviated toDAST) or reacted with tetrabutylammonium dihydrogen trifluoride orHF-pyridine in the presence of an oxidizing agent such asN-bromosuccinimide (hereinafter abbreviated to NBS) and1,3-dibromo-5,5-dimethylhidantoin (hereinafter abbreviated to DBH)according to a method described in Laid-open Japanese Patent PublicationNo. Hei 5-255165 to produce the objective compounds (1-B).

wherein R¹, X¹, Y¹, and rings A¹, A², and A⁴ have the same meaning asdescribed above.

The thion-O-ester derivatives (17) can also be produced by derivingdithiocarboxylic acid derivatives (16) into alkali metal salts and thenreacting with an alcolate or phenolate in the presence of iodine.Further, the ester derivatives (17) can be produced by reacting theester derivatives (1-A) obtained by the production method describedabove with 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulf ide (hereinafter abbreviated toLawesson's reagent).

Compounds expressed by the general formula (1) wherein X¹, X², or X³ isan ethenylene group, for example, compounds (1-C) expressed by thegeneral formula (1) wherein m is 1, n is 0, X¹ is —CH═CH—, and X² is—CF₂O—, and compounds (1-D) wherein X² is —COO— can preferably beproduced by the following method. That is, first, E,Z-olefin mixtures(22) are obtained by reacting ylides prepared by reacting the Wittigreagent (19), which can be prepared from bromomethane derivatives (18)and triphenylphosphine according to a method described in OrganicReactions, Vol. 14, Chapter 3, with a base such as a sodium alkoxide andan alkyl lithium in tetrahydrofuran (hereinafter abbreviated as THF)with aldehyde derivatives (21). Next, the E,Z-olefin mixtures arereacted with benzene sulfinic acid or ptoluenesulfinic acid according toa method described in Japanese patent publication No. Hei 4-30382 toisomerize. A¹ ternatively, E,Z-olefin mixtures are reacted withm-chloroperbenzoic acid according to a method described in Japanesepatent Publication No. Hei 6-62462 to convert into oxylane derivatives(23). The oxylane derivatives are then reacted with dibromotriphenylphosphorane to derive into dibromo derivatives (24). Subsequently, thederivatives (24) are subjected to recrystallization to purify onlyerithro isomer and then reduced with metal zinc to produce E-olefinderivatives (25). The objective compounds (1-C) can be produced bytreating the derivatives (25) in the same manner as in the compounds(1-B) described above.

wherein R¹ , Y¹, and rings A¹, A², and A⁴ have the same meaning asdescribed above.

On the other hand, carboxylic acid derivatives (26) can be produced bylithiating the compounds (25) obtained by the procedures described abovewith butyl lithium or the like, and then reacting with carbon dioxide.The objective compounds (1-D) can be produced by treating the compounds(26) in the same manner as in the case of producing compounds (1-C).

wherein R¹,Y¹, and rings A¹, A², and A⁴ have the same meaning asdescribed above.

Compounds expressed by the general formula (1) wherein X¹, X², or X³ isethynylene group, for examples, compounds (1-E) expressed by the generalformula (1) wherein m is 1, n is 0, X¹ is —C≡C—, and X² is —CF₂O—, andcompounds (1-F) wherein X² is —COO— can preferably be produced by thefollowing methods. That is, acetylene derivatives (27) are reacted withcompounds (28) in the presence of a catalyst according to a methoddescribed in J. Org. Chem., 28, 2163, 3313 (1963) to produce compounds(29). The objective compounds (1-E) can be produced by treating thecompounds (29) thus obtained in the same manner as in the case ofproducing the compounds (1-B) described above.

wherein R¹, Y¹, and rings A¹, A², and A⁴ have the same meaning asdescribed above.

On the other hand, carboxylic acid derivatives (30) can be produced bylithiating the compounds (29) obtained by the procedures described abovewith butyl lithium or the like, and then reacting with carbon dioxide.The objective compounds (1-F) can be produced by treating the compounds(30) in the same manner as in the case of producing the compounds (1-C)described above.

wherein R¹, Y¹, and rings A¹, A², and A⁴ have the same meaning asdescribed above.

Acetylene derivatives (27) can readily be produced by treatingdibromides (31), which can easily be produced by adding bromine tocorresponding vinyl derivatives, with a base according to a methoddescribed in J. Org. Chem., 38, 1367 (1963).

wherein R¹ and ring A¹ have the same meaning as described above.

Besides, other compounds which are not described above can preferably beproduced by properly selecting various methods described in well knownreference books on organic synthesis or patent publications andcombining the methods.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the methods for producing the compounds of the present inventionand the methods for using the compounds are described in more detailwith reference to Examples. In each of the Examples, Cr indicatescrystal; N, nematic phase; Sm, smectic phase; and Iso, isotropic liquid,and the unit of all phase transition temperatures is ° C. In lH-NMR, sindicates singlet; d, doublet; t, triplet; and m, multiplet; and Jindicates coupling constant (Hz). Further, in mass spectrum (GC-MS),M+indicates molecular ion peak.

EXAMPLE 1

Preparation of 2,3-difluoro-4-ethoxyphenyl2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)benzoate (Compoundexpressed by the general formula (1) wherein m is 1, n is 0, ring A¹represents trans-1,4-cyclohexylene group, ring A² represents2-fluoro-1,4-phenylene group, ring A⁴ represents2,3-difluoro-1,4-phenylene group, X¹ represents —CH₂CH₂-, R¹ representsn—C₃H₇, and Y¹ represents OC₂H₅; Compound No. 15)

(First step)

First, 100 g (0.77 mol) of 2,3-difluorophenol, 100 g (0.92 mol) of ethylbromide, 127 g (0.92 mol) of potassium carbonate, 1.0 g (6.0 inmol) ofpotassium iodide, and 1.3 l of dimethyl-formamide (DMF) were mixed andheated to reflux for 7 hours. After finishing of the reaction, 1.0 Q ofwater was added to the reaction solution and then extracted with 2.0 Qof toluene. The organic layer thus obtained was washed with water onceand then dried over anhydrous magnesium sulfate. The solvent wasdistilled off under a reduced pressure and the residue was distilledunder a reduced pressure to obtain 87.5 g of 2,3-difluoroethoxybenzene(yield 71.4%).

(Second step)

To a solution prepared by dissolving 19.0 g (0.12 mol) of the2,3-difluoroethoxybenzene obtained by the first step, in 250 ml oftetrahydrofuran (THF) was added dropwise 100 ml of solution of 1.56 M ofn-butyl lithium in hexane at −78° C. in 30 min and stirred as it was for30 min. To this solution was added dropwise solution of 25 g (0.24 mol)of trimethyl borate in 50 ml of THF at the same temperature in 10 min,stirred at the same temperature for 3 hours, and then gradually warmedup to room temperature. To this solution was added 55.2 g (1.2 mol) offormic acid, further 108.8 g of 30% by weight of hydrogen peroxide wasadded in 30 min, and then the solution was heated up to 50° C. andstirred as it was for 30 min. After the reaction solution was allowed tostand to cool down to room temperature, the solution was poured into 5%by weight of aqueous sodium thiosulfate solution and extracted with 400ml of toluene. The organic layer was dried over anhydrous magnesiumsulfate, the solvent was distilled off under a reduced pressure, and theresidue was recrystallized from heptane to obtain 9.1 g of2,3-difluoro-4-ethoxyphenol (yield 43.4%)

(Third step)

First, 1.7 g (10 mmol) of the 2,3-difluoro-4-ethoxyphenol obtained bythe second step, 2.9 g (10 mmol) of2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)benzoic acid, 1.3 g (11mmol) of DMAP, and 100 ml of dichloromethane were mixed. To this mixturewas added dropwise solution of 2.27 g (11 mmol) of DCC in 15 ml ofdichloromethane under a condition cooled with ice in 10 min, and thenthe mixture was warmed up to room temperature and stirred as it wasovernight. Separated crystals were filtered off and the solvent wasdistilled off under a reduced pressure from the filtrate. The residuewas purified by silica gel column chromatography (eluent: ethyl acetate)and further recrystallized from heptane to obtain 2.48 g of the subjectcompound (yield 55.3%).

This compound exhibited liquid crystal phase and its phase transitiontemperatures were as follows:

C-N point: 65.4, N-I point: 141.3

Data of various kind of spectrums supported the structure of thecompound described above.

¹H-NMR (CDCl₃); δ (ppm): 8.09-7.92 (t, 1H, J=15.7 Hz), 7.11-6.75 (m,4H), 4.25-4.02 (q, 2H, J=21.2 Hz), 2.78-2.61 (t, 2H, J=15.7 Hz),1.81-0.88 (m, 22H) Mass spectrum: 448 (M⁺).

EXAMPLE 2

Preparation of(2,3-difluoro-4-ethoxyphenyl)oxy(4-(trans-4-n-pentylcyclohexyl)phenyl)difluoromethane(Compound expressed by the general formula (1) wherein m is 1, n is 0,ring A¹ represents trans-1,4-cyclohexylene group, ring A² represents1,4-phenylene group, ring A⁴ represents 2,3-difluoro-1,4-phenylenegroup, X¹ represents single bond, X² represents —CF₂O—, R¹ representsn—C₅H₁₁, and Y¹ represents OC₂H₅; Compound No. 152)

(First step)

To a suspension prepared by suspending 0.95 g (39 mmol) of magnesium in200 ml of THF was added dropwise a solution prepared by dissolving 9.28g (30 mmol) of 4-(trans-4-n-pentylcyclohexyl) bromobenzene in 80 ml ofTHF, at room temperature while being stirred in 1 hour, and then heatedto reflux for 2 hours to prepare a Grignard reagent. To this solutionwas added dropwise 5.7 g (75 mmol) of carbon disulfide at roomtemperature in 30 min and stirred as it was overnight. To this reactionsolution was added 150 ml of 1M hydrochloric acid to terminate thereaction and extracted with 350 ml of toluene. The organic layer wasdried over anhydrous magnesium sulfate, the solvent was distilled offunder a reduced pressure, and the residue was recrystallized fromheptane to obtain 4.74 g of4-(trans-4-n-pentylcyclohexyl)phenyldithiocarboxylic acid (yield 51.5%).

(Second step)

To a suspension prepared by suspending 1.52 g (38.0 mmol) of 60% sodiumhydride in 15 ml of THF was added dropwise solution of 5.29 g (17.3mmol) of the 4-(trans-4-n-pentylcyclohexyl)-phenyldithiocarboxylic acidobtained by the first step, in 20 ml of THF under a condition cooledwith ice in 15 min, and stirred as it was for 30 min. To this reactionsolution was added dropwise solution of 2.50 g (14.4 mmol) of2,3-difluoro-4-ethoxyphenol in 20 ml of THF in 15 min and stirred as itwas for 30 min. To this reaction solution was added dropwise solution of9.64 g (38.0 mmol) of iodine in 20 ml of THF in 15 min, stirred as itwas for 1 hour, warmed up to room temperature, and then stirred at thesame temperature overnight. This reaction solution was poured into 10%aqueous sodium thiosulfate solution and extracted with 100 ml of diethylether. The organic layer was dried over anhydrous magnesium sulfate, thesolvent was distilled off under a reduced pressure, and the residue waspurified by silica gel column chromatography (eluent: heptane) andfurther recrystallized from heptane to obtain 2.0 g of2,3-difluoro-4-ethoxyphenyl 4-(trans-4-n-pentylcyclohexyl)thiobenzoate(yield 31.2%).

(Third step)

To a suspension prepared by suspending 1.59 g (8.93 mmol) ofN-bromosuccinimide in 20 ml of methylene chloride was added. dropwise1.78 g of hydrogen fluoride-pyridine at −78° C. in 15 min and stirred asit was for 10 min. To this reaction solution was added dropwise solutionof 2.0 g (4.48 mmol) of 2,3-difluoro-4-ethoxyphenyl4-(trans-4-n-pentylcyclohexyl)thiobenzoate in 30 ml of methylenechloride in 30 min and stirred as it was for 2 hours. This reactionsolution was poured into saturated aqueous sodium carbonate solution toterminate the reaction. The methylene chloride layer was separated, andwashed with 10% aqueous sodium bisulfite solution and water in turn, anddried over anhydrous magnesium sulfate. The solvent was distilled offunder a reduced pressure and the residue was purified by silica gelcolumn chromatography (eluent: heptane) to obtain 0.72 g of the subjectcompound (yield 35.5%).

This compound exhibited liquid crystal phase and its phase transitiontemperatures were as follows:

C-N point: 61.4, N-I point: 131.4

Data of various kind of spectrums supported the structure of thecompound described above.

¹H-NMR (CDCl₃). δ (ppm): 7.71-6.57 (m, 6H), 4.26-4.00 (q, 2H, J=21.0Hz), 2.53-2.83 (m, 24H) . ¹⁹F-NMR (CDCl13). δ (ppm): −66.5 (s, —CF₂O—).

Mass spectrum: 452 (M⁺).

EXAMPLE 3

Preparation of difluoro-(4-pentylphenyloxy)(4-(trans-4-propylcyclohexyl)phenyl)methane (Compound expressed by thegeneral formula (1) wherein m is 1, n is 0, ring A¹ representstrans-1,4-cyclohexylene group, ring A² represents 1,4-phenylene group,ring A⁴ represents 1,4-phenylene group, X¹ represents single bond, X²represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ represents C₅H₁;Compound No. 331)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 2.7 g (112.1 mmol) of turnings of magnesiumwere suspended in 50 ml of THF while being stirred under nitrogen gasatmosphere, and 70 ml of solution of 30 g (106.8 mmol) of4-(trans-4-propylcyclohexyl)bromobenzene in THF was added dropwise in 40min so that the internal temperature did not exceed 50° C. The reactionsolution was stirred while being heated at 50° C. with a hot water bathfor 2 hours to age. After the solution was cooled with an ice bath tolower the internal temperature down to 5° C., 24.4 g (320.4 mmol) ofcarbon disulfide was added dropwise in 25 min so that the internaltemperature did not exceed 10° C. The reaction solution was stirredwhile being maintained at a temperature lower than 10° C. for 30 min,warmed up to room temperature, and then stirred for 1 hour. The reactionsolution was cooled down to a temperature lower than 5° C. again, 25 mlof 6N hydrochloric acid was added thereto to terminate the reaction, andthen extracted with 400 ml of diethyl ether. The organic layer waswashed with 300 ml of an ice water and dried over anhydrous magnesiumsulfate. Diethyl ether was distilled off and the residue wasconcentrated to obtain 23.7 g of a deep purplish red (murex) solid. Thisproduct was 4-(trans-4-propylcyclohexyl)-phenyldithiocarboxylic acid.

(Second step)

In a 500 ml eggplant type flask, 23.7 g of the4-(trans-4-propylcyclohexyl)phenyldithiocarboxylic acid obtained by theprocedures described above was dissolved in 200 ml of diethyl ether,50.8 g of thionyl chloride was added thereto, and then the solution washeated on a hot water bath to reflux for 8 hours. The diethyl ether andunreacted thionyl chloride were distilled off under a reduced pressureproduced with an aspirator, and the residue was concentrated to obtain25 g of a deep murex oily substance. This substance was thioncarboxylicacid chloride derivative. Subsequently, in a 500 ml three-necked flaskprovided with a stirrer, thermometer, and nitrogen gas inlet tube, 21.0g (128.2 mmol) of 4-pentylphenol and 10.1 g (128.1 mmol) of pyridinewere dissolved in 30 ml of toluene under nitrogen gas atmosphere, and 70ml of solution of 25.0 g of the thioncarboxylic acid chloride derivativeobtained by the procedures described above in toluene was added theretowhile being stirred the solution at room temperature in 20 min. Afterfinishing of the dropping, the reaction solution was heated on a hotwater bath so that the internal temperature rose up to 60° C. and thenstirred for 3 hours to age. After the reaction solution was cooled downto room temperature, 100 ml of water and 30 ml of 6N hydrochloric acidwere added to the reaction solution, the toluene layer was separated,and then the water layer was extracted with 200 ml of toluene. Thetoluene layers were coalesced, washed with 200 ml of water, 80 ml of 2Naqueous sodium hydroxide solution, and 300 ml of water in turn, and thendried over anhydrous magnesium sulfate. The toluene was distilled offunder a reduced pressure to obtain 28.3 g of a deep murex past likeresidue. The residue was purified by silica gel column chromatography(eluent: heptane) and further recrystallized from heptane to obtain 12.7g of pale yellow needle-shaped crystals of 4-pentylphenyl4-(trans-4-n-propylcyclohexyl)thiobenzoate.

(Third step)

In a 300 ml eggplant type flask, 5.0 g (12.3 mmol) of the 4-pentylphenyl4-(trans-4-n-propylcyclohexyl)thiobenzoate obtained by the proceduresdescribed above was dissolved in 60 ml of dichloromethane under nitrogengas stream, 7.9 g (49.0 mmol) of DAST was added thereto at roomtemperature, and then the solution was stirred for 25 hours. Thereaction solution was added to 200 ml of an ice water to terminate thereaction, the dichloromethane layer was separated, and further the waterlayer was extracted with 100 ml of dichloromethane. The dichloro-methane layers were coalesced, washed with 200 ml of water, 50 ml of 2Naqueous sodium hydroxide solution, and 200 ml of water in turn, and thendried over anhydrous magnesium sulfate. The dichloromethane wasdistilled off and the residue was concentrated to obtain 3.8 g of a paleyellow crystalline crude product. This crude product was purified bysilica gel column chromatography (eluent: heptane) and thenrecrystallized from heptane to obtain 1.7 g of colorless needle-shapedcrystals of difluoro-(4-pentylphenyloxy)(4-(trans-4-propylcyclohexyl)-phenyl)methane. Data of various kind ofspectrums supported the structure of the compound described above.

Mass spectrum: 414 (M⁺).

EXAMPLE 4

Preparation of difluoro-(4-(trans-4-ethenylcyclohexyl)-phenyloxy)(4-propylphenyl)methane (Compound expressed by the general formula (1)wherein m is 1, n is 0, both ring A¹ and ring A² represent 1,4-phenylenegroup, ring A⁴ represents trans-1,4-cyclohexylene group, X¹ represents—CF₂O—, X² represents single bond, R¹ represents n—C₃H₇, and Y¹represents vinyl group; Compound No. 441)

Preparation process can broadly be divided into three stages of 1)synthesis of 4-(4-hydroxyphenyl)cyclohexanone, 2) synthesis ofcyclohexanone intermediate (32), and 3) preparation ofdifluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy)(4-propylphenyl)methane. The process is described in detail below witheach preparation stage being separated. 1) [Synthesis of4-(hydroxyphenyl)cyclohexanone]

(First step)

In a 1 Q three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 5.8 g (239.0 mmol) of turnings of magnesiumwere suspended in 100 ml of THF while being stirred under nitrogen gasatmosphere, and 200 ml of solution of 60 g (228.1 mmol) of4-bromophenoxybenzyl ether in THF was added dropwise thereto in 80 minso that the internal temperature did not exceed 50° C. The reactionsolution was stirred while being heated at 50° C. with a hot water bathfor 2 hours to age. Subsequently, 42.7 g (274.3 mmol) of1,4-cyclohexanedionemonoethyleneketal was added dropwise at roomtemperature to the reaction solution in 40 min so that the internaltemperature did not exceed 60° C. The reaction solution was stirred on ahot water bath while being maintained at 50° C. for 2 hours and thencooled with an ice water, and 100 ml of saturated aqueous ammoniumchloride solution was added thereto to terminate the reaction. Thereaction solution was extracted with 400 ml of toluene. The tolueneextract was washed with 900 ml of water and then dried over anhydrousmagnesium sulfate. The toluene was distilled off under a reducedpressure to obtain 73.6 g of a brown solid product. This product wasdissolved in 340 ml of toluene in a 1 Q eggplant type flask providedwith a Dean and Stark dehydrating tube, 5.9 g of non-aqueous acidic ionexchange resin (Amberlist) was added as acid catalyst thereto, and thesolution was heated to reflux for 3 hours while being stirred. After thecatalyst was removed by filtration, the toluene was distilled off undera reduced pressure, and the residue was purified by silica gel columnchromatography (eluent: toluene), and then recrystallized from tolueneto obtain 41.8 g of colorless needle-shaped crystals of cyclohexenederivative (33).

(Second step)

The cyclohexene derivative (33) obtained in the first step was dissolvedin 200 ml of mixed solvent of toluene/ethanol of 1/1 in a 1 Q eggplanttype flask, 2.5 g of 5% palladium-carbon catalyst was added thereto, andthe solution was subjected to a hydrogenation reaction at roomtemperature under a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours.After the catalyst was removed by filtration, the reaction solution wasconcentrated to obtain 30.2 g of a reaction product. This reactionproduct was dissolved in 100 ml of toluene in a 300 ml three-neckedflack provided with a stirrer and thermometer, 29.9 g of 99% formic acidwas added to the solution, and then the solution was heated to refluxwhile being stirred for 2 hours. Water in an amount of 300 ml was addedto the reaction solution, the toluene layer was separated, and furtherthe water layer was extracted with 200 ml of toluene. The toluene layerswere coalesced, washed with 800 ml of water, and then dried overanhydrous magnesium sulfate. The toluene was distilled off under areduced pressure to obtain 18.0 g of 4-(4-hydroxyphenyl)cyclohexanone.2) [Synthesis of cyclohexanone intermediate (32)]

(Third step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 18.0 g (94.8 mmol) of4-(4-hydroxyphenyl)cyclohexanone was dissolved in 30 ml of toluene undernitrogen gas atmosphere, 9.7 g (123.0 mmol) of pyridine was addedthereto, and then 50 ml of solution of 24.4 g (123.0 mmol) of the4-propylphenylthioncarboxylic acid chloride synthesized by the sameprocedures as in the first and second steps in Example 1, in toluene wasadded dropwise in 15 min. After finishing of the dropping, the reactionsolution was heated up to 60° C on a hot water bath and stirred for 3hours to age. After the reaction solution was cooled down to roomtemperature, 100 ml of water and 50 ml of 6N hydrochloric acid wereadded thereto,the toluene layer was separated, and then the water layerwas extracted with 200 ml of toluene. The toluene layers were coalesced,washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxidesolution, and 300 ml of water in turn, and then dried over anhydrousmagnesium sulfate. The toluene was distilled off under a reducedpressure to obtain 33.2 g of a deep murex paste like product. Thisproduct was purified by silica gel column chromatography (eluent: mixedsolvent of heptane/toluene=1/1) and further recrystallized from heptaneto obtain 18.4 g of pale yellow needle-shaped crystals. These crystalswere thioncarboxylic acid-O-ester derivative (34).

(Fourth step)

In a 300 ml eggplant type flask provided with a nitrogen gas inlet tube,18.4 g (52.0 mmol) of the thioncarboxylic acid-O-ester derivative (34)obtained by the procedures described above was dissolved in 250 ml ofdichloromethane under nitrogen gas atmosphere, 33.5 g (208.0 rnmol) ofDAST was added thereto at room temperature, and then the solution wasstirred for 25 hours. The reaction solution was added to 200 ml of anice water to terminate the reaction, the dichloromethane layer wasseparated, and further the water layer was extracted with 100 ml ofdichloromethane. The dichloromethane layers were coalesced, washed with200 ml of water, 50 ml of 2N aqueous sodium hydroxide solution, and 200ml of water in turn, and then dried over anhydrous magnesium sulfate.The dichloromethanewas distilled off to obtain 13,6 g of a pale yellowcrystalline crude product. This crude product was purified by silica gelcolumn chromatography (eluent: mixed solvent of heptane/toluene=1/1) andfurther recrystallized from heptane to obtain 8.0 g of colorlessneedle-shaped crystals. These crystals were cyclohexanone intermediate(32).

3) [Synthesis of difluoro-(4-(trans-4-ethenylcyclohexyl)-phenyloxy)(4-propylphenyl)methane]

(Fifth step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 9.8 g (28.6 mmol) ofmethoxymethyltriphenylphosphonium chloride was dissolved in 80 ml of THFunder nitrogen gas atmosphere and cooled down to a temperature lowerthan −50° C. with a dry ice-acetone bath, 3.4 g (30.0 mmol) ofpotassium-t-butoxide was added thereto, and then the solution wasstirred while being maintained at a temperature lower than −50° C. for 2hours to prepare an ylide. Then, 20 ml of solution of 8.0 g (22.0 mmol)of the cyclohexanone intermediate (32) obtained by the fourth stepdescribed above, in THF was added thereto at the same temperature in 10min, and stirred at the same temperature for 1 hour. Subsequently, thesolution was warmed up to room temperature and further stirred at roomtemperature for 8 hours. After 200 ml of water was added to the reactionsolution to terminate the reaction, the THF layer was separated, andfurther the water layer was extracted with 100 ml of toluene. Thetoluene layers were coalesced, washed with 500 ml of water, and thendried over anhydrous magnesium sulfate. The solvent was distilled offunder a reduced pressure to obtain 18.5 g of a crude product. This crudeproduct was purified by silica gel column chromatography (eluent:toluene) to obtain 7.6 g of a yellowish brown product. The product thusobtained was dissolved in 50 ml of toluene in a 200 ml eggplant typeflask, 5.3 g (114.0 mmol) of 99% formic acid was added thereto, and thesolution was heated to reflux for 2 hours. Water in an amount of 50 mlwas added to the reaction solution and extracted with 50 ml of toluene.The toluene layer was washed with 100 ml of water, 30 ml of 2N aqueoussodium hydroxide solution, and 100 ml of water in turn, and then driedover anhydrous magnesium sulfate. The solvent was distilled off under areduced pressure and 7.3 g of the residue thus obtained was purified bysilica gel column chromatography (eluent: toluene) to obtain 5.6 g ofcolorless crystalline cyclohexanecarbaldehyde derivative (35).

(Sixth step)

In a 200 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 7.0 g (17.4 mmol) of methyltriphenylphosphoniumiodide was suspended in 30 ml of THF under nitrogen gas atmosphere andcooled down to a temperature lower than −50° C. with a dry ice-acetonebath, and 2.1 g (18.3 mmol) of potassium-t-butoxide was added thereto,and then the suspension was stirred while being maintained at atemperature lower than −50° C. for 2 hours to prepare a ylide. Then, 15ml of solution of 5.0 g (13.4 mmol) of the cyclohexanecarboaldehydederivative (35) obtained by the fifth step, in THF was added dropwisethereto at the same temperature in 5 min, stirred at the sametemperature for 1 hour, warmed up to room temperature, and furtherstirred for 8 hours. Water in an amount of 50 ml was added to thereaction solution to terminate the reaction, the THF layer wasseparated, and further the water layer was extracted with 50 ml oftoluene. The THF layer and the toluene layer were coalesced, washed with80 ml of water, and then dried over anhydrous magnesium sulfate. Thesolvent was distilled off under a reduced pressure, and 4.8 g of theproduct thus obtained was purified by silica gel column chromatography(eluent: heptane) and further recrystallized from heptane to obtain 2.4g of a colorless needle-shaped compound. This compound was the objectivedifluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy)(4-propylphenyl)methane. Data of various kind of spectrums supported thestructure of the compound described above.

Mass spectrum: 370 (M⁺).

EXAMPLE 5

Preparation of difluoro-(4-(trans-4-(3-butenyl)cyclohexyl)-phenyloxy)(4-propylphenyl)methane (Compound expressed by the general formula (1)wherein m is 1, n is 0, both ring A¹ and ring A² represent 1,4-phenylenegroup, ring A⁴ represents trans-1,4-cyclohexylene group, X¹ represents—CF₂O—, X² represents single bond, R¹ represents n—C₃H₇, and Y¹represents 3-butenyl; Compound No. 442)

(First step)

In a 100 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 12.8 g (29.1 mmol) of2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide was suspended in40 ml THF under nitrogen gas atmosphere and cooled down to a temperaturelower than −50° C. with a dry ice-acetone bath, 3.4 g (30.5 mmol) ofpotassium-t-butoxide was added to the suspension, and then thesuspension was stirred while being maintained at a temperature lowerthan −50° C. for 2 hours to prepare a ylide. Then, 30 ml of solution of8.0 g (22.4 mmol) of the cyclohexanone intermediate (32) described inExample 4, in THF was added dropwise thereto at the same temperature in20 min, stirred at the same temperature for 1 hour, warmed up to roomtemperature, and further stirred for 8 hours. Water in an amount of 50ml was added to the reaction solution to terminate the reaction, the THFlayer was separated, and the water layer was extracted with 100 ml oftoluene. The THF layer and the toluene layer were coalesced, washed with200 ml of water, and then dried over anhydrous magnesium sulfate. Thesolvent was distilled off under a reduced pressure, and 15.5 g of theresidue thus obtained was purified by silica gel column chromatography(eluent: mixed solvent of toluene/ethyl acetate) to obtain 8.2 g ofyellowish brown crystals. Subsequently, these yellowish brown crystalswere dissolved in 60 ml of mixed solvent of toluene/ethanol of 1/1 in a200 ml eggplant type flask, 0.4 g of 5% palladium-carbon catalyst wasadded thereto, and then the solution was subjected to a catalytichydrogen reduction at room temperature under a condition of hydrogen gaspressure of 1 to 2 kg/cm² until the time when absorption of hydrogenceased. The catalyst was removed from the reaction solution byfiltration and then the solvent was distilled off under a reducedpressure to obtain 7.4 g of a product. This product was dissolved in 30ml of toluene in a 100 ml of eggplant type flask, 3.9 g (83.5 mmol) of99% formic acid was added thereto, and then the solution was heated toreflux for 2 hours. Water in an amount of 50 ml was added to thereaction solution, the toluene layer was separated, and further thewater layer was extracted with 60 ml of toluene. The toluene layers werecoalesced, washed with 100 ml of water, 30 ml of 2N aqueous sodiumhydroxide solution, and 100 ml of water in turn, and then dried overanhydrous magnesium sulfate. The toluene was distilled off under areduced pressure, and 7.0 g of the residue thus obtained was purified bysilica gel column chromatography (eluent: toluene) to obtain 5.9 g ofyellowish brown crystalline aldehyde derivative (36).

(Second step)

In a 100 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 7.8 g (19.3 mmol) of methyltriphenylphosphoniumiodide was suspended in 30 ml of THF under nitrogen gas atmosphere andcooled down to a temperature lower than −50° C. with a dry ice-acetonebath, 2.2 g (20.3 mmol) of potassium-t-butoxide was added thereto, andthen the suspension was stirred while being maintained at a temperaturelower than −50° C. for 2 hours to prepare a ylide. Then, 20 ml ofsolution of 5.9 g (14.9 mmol) of the aldehyde derivative (36) obtainedby the first step, in THF was added dropwise at the same temperaturethereto in 5 min, stirred at the same temperature for 1 hour, warmed upto room temperature, and further stirred for 8 hours. Water in an amountof 50 ml was added to the reaction solution to terminate the reaction,the THF layer was separated, and the water layer was extracted with 100ml of toluene. The THF layer and the toluene layer were coalesced,washed with 200 ml of water, and then dried over anhydrous magnesiumsulfate. The solvent was distilled off under a reduced pressure, and 5.6g of the product thus obtained was purified by silica gel columnchromatography (eluent: heptane) and further recrystallized from heptaneto obtain 2.4 g of colorless needle-shaped crystals. These crystals werethe objective difluoro-(4-(trans-4-(3-butenyl)cyclohexyl)phenyloxy)(4-propylphenyl)methane. Data of various kind of spectrums supported thestructure of the compound described above.

Mass spectrum: 398 (M⁺).

EXAMPLE 6

Preparation of difluoro-(4-(trans-4-propylcyclohexyl)-phenyloxy)(4-(trans-4-pentylcyclohexyl)phenyl)methane (Compound expressed by thegeneral formula (1) wherein m and n are 1, both ring A¹ and ring A⁴represent trans-1,4-cyclohexylene group, both A² and ring A³ represent1,4-phenylene group, both X¹ and X³ represent single bond, X² represents—CF₂O—, R¹ represents n—C₅H₁, and Y¹ represents n—C₃H₇; Compound No.572)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 4.2 g (172.7 mmol) of turnings of magnesiumwere suspended in 50 ml of THF under nitrogen gas atmosphere, and 120 mlof solution of 50 g (161.7 mmol) of4-(trans-4-pentylcyclohexyl)bromobenzene in THF was added dropwisethereto while the internal temperature being maintained at 50° C. on ahot water bath in 40 min. The reaction solution was stirred while beingheated at 50° C. with a hot water bath for 2 hours to age. Then, thecontents of the flask were cooled with an ice bath so that the internaltemperature lowered down to 5° C., and 61.6 g (809.0 mmol) of carbondisulfide was added dropwise in 35 min so that the internal temperaturedid not exceed 10° C. The reaction solution was stirred while beingmaintained at a temperature lower than 10° C. for 30 min, warmed up toroom temperature, and then stirred for 2 hours. The reaction solutionwas cooled down again to a temperature lower than 5° C., 100 ml of 6Nhydrochloric acid was added thereto to terminate the reaction, and thenextracted with 800 ml of diethyl ether. The diethyl ether layer waswashed with 800 ml of an ice water and then dried over anhydrousmagnesium sulfate. The diethyl ether was distilled off to obtain 50.8 gof a deep murex solid. This solid was4-(trans-4-pentylcyclohexyl)phenyl-dithiocarboxylic acid.

(Second step)

In a 500 ml eggplant type flask, 50.8 g of the4-(trans-4-pentylcyclohexyl)phenyldithiocarboxylic acid obtained by theprocedures described above was dissolved in 300 ml of diethyl ether,115.6 g (971.6 mmol) of thionyl chloride was added thereto at roomtemperature, and then the solution was heated on a hot water bath toreflux for 8 hours. The diethyl ether and unreacted thionyl chloridewere distilled off under a reduced pressure produced with an aspiratorto obtain 66.8 g of a deep murex paste like substance. This substancewas thioncarboxylic acid chloride derivative.

Subsequently, in a 500 ml three-necked flask provided with a stirrer,thermometer, and nitrogen gas inlet tube, 17.2 g (78.8 mmol) of4-(trans-4-propylcyclohexyl)phenol and 5.7 g (72.2 mmol) of pyridinewere dissolved in 80 ml of toluene under nitrogen gas atmosphere, and 60ml of solution of 20.3 g of the thioncarboxylic acid chloride derivativeobtained by the procedures described above, in toluene was addeddropwise thereto in 20 min. After finishing of the dropping, thereaction solution was heated up to 60° C. on a hot water bath andstirred for 3 hours to age. After the reaction solution was cooled downto room temperature, 200 ml of water and 80 ml of 6N hydrochloric acidwere added to the reaction solution, the toluene layer was separated,and further the water layer was extracted with 300 ml of toluene. Thetoluene layers were coalesced, washed with 400 ml of water, 80 ml of 2Naqueous sodium hydroxide solution, and 400 ml of water in turn, and thendried over anhydrous magnesium sulfate. The toluene was distilled offunder a reduced pressure, and 31.9 of a deep murex paste like productthus obtained was purified by silica gel column chromatography (eluent:mixed solvent of heptane/toluene) and recrystallized from heptane toobtain 5.8 g of pale yellow needle-shaped crystals. These crystals werethioncarboxylic acid-O-ester derivative (37).

Phase transition temperatures: Cr 136.2 N 263.6 Iso; ¹H-NMR δ (ppm):0.8-2.1 (36H, m), 2.3-2.7 (2H, m), 7.0 (2H, d, J=8.6 Hz), 7.2-7.3 (4H,bd), and 8.3 (2H, d, J=8.3 Hz)

(Third step)

In a 100 ml eggplant type flask, 5.8 g (11.9 mmol) of thethioncarboxylic acid-O-ester derivative (37) obtained by the proceduresdescribed above was dissolved in 60 ml of dichloromethane under nitrogengas stream, and 9.6 g (59.5 mmol) of DAST was added thereto at roomtemperature and stirred for 25 hours. The reaction solution was added to200 ml of an ice water to terminate the reaction, the dichloromethanelayer was separated, and further the water layer was extracted with 100ml of dichloromethane. The dichloromethane layers were coalesced,.washed with 200 ml of water, 50 ml of 2N aqueous sodium hydroxidesolution, and 200 ml of water in turn, and then dried over anhydrousmagnesium sulfate. The dichloromethane was distilled off, and 7.6 g of apale yellow crystalline mixture thus obtained was purified by silica gelcolumn chromatography (eluent: heptane) and further recrystallized fromheptane to obtain 1.9 g of colorless needle-shaped crystals. Thesecrystals were the objectivedifluoro-(4-(trans-4-propylcyclohexyl)phenyloxy)(4-(trans-4-pentylcyclohexyl)-phenyl)methane. Data of various kind ofspectrums supported the structure of the compound described above.

Phase transition temperatures: S_(A) 106.3 N˜170.0 Iso (decomposed).¹H-NMR δ (ppm): 0.8-2.1 (36H, m), 2.3-2.8 (2H, m), 7.2 (4H, S), 7.2-7.3(2H, bd), and 7.6 (2H, d, J=8.3 Hz). Mass spectrum: 496 (M⁺).

EXAMPLE 7

Preparation of difluoro-(4-(trans-4-ethenylcyclohexyl)-phenyloxy)(4-(trans-4-propylcyclohexyl)phenyl)methane (Compound expressed by thegeneral formula (1) wherein m and n are 1, both ring A¹ and ring A⁴represent trans-1,4-cyclohexylene group, both ring A² and ring A³represent 1,4-phenylene group, both X¹ and X³ represent single bond, X²represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ represents vinyl group;Compound No. 573)

(First step)

In a 500 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 14.1 g (74.3 mmol) of the4-(4-hydroxyphenyl)cyclohexanone prepared by Example 4 (first and secondsteps) and 7.4 g (93.7 mmol) of pyridine were dissolved in 50 ml oftoluene under nitrogen gas atmosphere, and 60 ml of solution of 25.0 g(89.2 mmol) of the thioncarboxylic acid chloride derivative prepared byExample 3 (first and second steps), in toluene was added dropwise whilebeing stirred at room temperature in 20 min. After finishing of thedropping, the reaction solution was heated up to 60° C. on a hot waterbath and stirred for 3 hours to age. The reaction solution was cooleddown to room temperature, 200 ml of water and 80 ml of 6N hydrochloricacid were added to the solution, the toluene layer was separated, andfurther the water layer was extracted with 300 ml of toluene. Thetoluene layers were coalesced, washed with 400 ml of water, 80 ml of 2Naqueous sodium hydroxide solution, and 400 ml of water in turn, and thendried over anhydrous magnesium sulfate. The toluene was distilled offunder a reduced pressure, and 38.2 g of the deep murex paste likeproduct thus obtained was purified by silica gel column chromatography(eluent: mixed solvent of heptane/toluene) and further recrystallizedfrom heptane to obtain 14.3 g of pale yellow needle-shaped crystals.These crystals were thioncarboxylic acid—O—ester derivative (38).

(Second step)

In a 100 ml eggplant type flask, 14.3 g (32.9 mmol) of thethioncarboxylic acid-O-ester derivative (38) obtained by the proceduresdescribed above was dissolved in 100 ml of dichloromethane undernitrogen gas atmosphere, and 26.5 g (164.7 mmol) of DAST was addedthereto at room temperature and stirred for 25 hours. The reactionsolution was added to 300 ml of an ice water to terminate the reaction,the dichloromethane layer was separated, and further the water layer wasextracted with 200 ml of dichloromethane. The dichloromethane layerswere coalesced, washed with 500 ml of water, 80 ml of 2N aqueous sodiumhydroxide solution, and 500 ml of water in turn, and then dried overanhydrous magnesium sulfate. The dichloromethane was distilled off, and14.1 g of a pale yellow crystalline mixture thus obtained was purifiedby silica gel column chromatography (eluent: toluene) and furtherrecrystallized from heptane to obtain 7.1 g of colorless needle-shapedcrystals. These crystals were cyclohexanone derivative (39).

(Third step)

In a 300 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 6.9 g (20.1 mmol) ofmethoxymethyl-triphenylphosphonium chloride was suspended in 50 ml ofTHF under nitrogen gas atmosphere and cooled down to a temperature lowerthan −50° C. with a dry ice-acetone bath, 2.4 g (21.1 mmol) ofpotassium-t-butoxide was added thereto, and then the suspension wasstirred while being maintained at a temperature lower than −50° C. for 2hours to prepare a ylide. Then, 20 ml of solution of 7.1 g (16.1 mmol)of the cyclohexanone derivative (39) obtained by the second step, in THFwas added dropwise thereto in 10 min at the same temperature, stirred atthe same temperature for 1 hour, warmed up to room temperature, and thenfurther stirred for 8 hours. Water in an amount of 100 ml was added tothe reaction solution to terminate the reaction, the THF layer wasseparated, and further the water layer was extracted with 100 ml oftoluene. The THF layer and the toluene layer were coalesced, washed with200 ml of water, and then dried over anhydrous magnesium sulfate. Thesolvent was distilled off, and 14.1 g of the product thus obtained waspurified by silica gel column chromatography (eluent: toluene) to obtain6.8 g of a yellowish brown reaction product.

Subsequently, in a 200 ml eggplant type flask, the reaction product wasdissolved in 40 ml of toluene, 4.1 g (88.2 mmol) of 99% formic acid wasadded thereto, and the solution was heated to reflux for 2 hours. Waterin an amount of 50 ml was added to the reaction solution and extractedwith 50 ml of toluene, the extract layer was washed with 100 ml ofwater, 30 ml of 2N aqueous sodium hydroxide solution, and 100 ml ofwater in turn, and then dried over anhydrous magnesium sulfate. Thesolvent was distilled off under a reduced pressure, and 9.8 g of theproduct thus obtained was purified by silica gel column chromatography(eluent: toluene) to obtain 4.7 g of colorless crystals. These crystalswere cyclohexanecarbaldehyde derivative (40).

(Fourth step)

In a 200 ml three-necked flask provided with a stirrer, thermometer, andnitrogen gas inlet tube, 5.2 g (12.9 mmol) of methyltriphenylphosphoniumiodide was suspended in 30 ml of THF under nitrogen gas atmosphere andcooled down to a temperature lower than −50° C. with a dry ice-acetonebath, 1.5 g (13.5 mmol) of potassium-t-butoxide was added thereto, andthen the suspension was stirred while being maintained at a temperaturelower than −50° C. for 2 hours to prepare a ylide. Then, 15 ml ofsolution of 4.7 g (10.4 mmol) of the cyclohexanecarbaldehyde derivative(40) obtained by the procedures described above in THF was addeddropwise thereto at the same temperature in 5 min, stirred for 1 hour atthe same temperature, warmed up to room temperature, and further stirredfor 8 hours. Water in an amount of 50 ml was added to the reactionsolution to terminate the reaction, the THF layer was separated, and thewater layer was extracted with 50 ml of toluene. The THF layer and thetoluene layer were coalesced, washed with 80 ml of water, and then driedover anhydrous magnesium sulfate. The solvent was distilled off under areduced pressure, and 6.4 g of the product thus obtained was purified bysilica gel column chromatography (eluent: heptane) and furtherrecrystallized from heptane to obtain 1.5 g of a colorless needle-shapedcompound. This compound was the objectivedifluoro-(4-(trans-4-ethenylcyclohexyl)phenyloxy)(4-(trans-4-propylcyclohexyl)phenyl)methane. Data of various kind ofspectrums supported the structure of the compound described above.

Mass spectrum: 452 (M⁺).

EXAMPLE 8

Preparation of(2,3-difluoro-4-ethoxyphenyl)oxy(trans-4-(trans-4-n-propylcyclohexyl)cyclohexyl)difluoromethane(Compound expressed by the general formula (1) wherein m is 1, n is 0,both rings A¹ and ring A² represent trans-1,4-cyclohexylene group, ringA⁴ represents 2,3-difluoro-1,4-phenylene group, X¹ represents singlebond, X² represents —CF₂O—, R¹ represents n—C₃H₇, and Y¹ representsOC₂H₅; Compound No. 144)

(First step)

First, 10.0 g (57.5 mmol) of the 2,3-difluoro-4-ethoxyphenol obtained bythe method described in the second step of Example 1, 17.4 g (68.9 mmol)of trans-4-(trans-4-propylcyclohexyl)-cyclohexanecarboxylic acid, 0.2 g(1.8 mmol) of DMAP, and 300 ml of dichloromethane were mixed. To thismixture was added dropwise 80 ml of solution of 12.3 g (60.0 mmol) ofDCC in dichloromethane under a condition cooled with ice in 10 min,warmed up to room temperature, and then stirred as it was overnight.Separated crystals were removed by filtration, the solvent was distilledof under a reduced pressure from the filtrate, and the residue thusobtained was purified by silica gel column chromatography (eluent:toluene) and further recrystallized from heptane to obtain 20.8 g of2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-propylcyclohexyl)benzoate.

(Second step)

In a 300 ml sealed glass tube, 20.8 g (50.9 mmol) of the2,3-difluoro-4-ethoxyphenyl trans-4-(trans-4-propylcyclohexyl)-benzoatewas dissolved in 150 ml of toluene, 24.7 g (61.1 mmol) of Lawesson'sreagent was added thereto, and then the solution was heated at 140° C.on an oil bath for 8 hours. Water in an amount of 200 ml was added tothe reaction solution and then the toluene layer was separated. Thetoluene layer was washed with 150 ml of water thrice and then dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure, and the brown residue thus obtained was purified bysilica gel column chromatography (eluent: mixed solvent ofheptane/toluene) and then recrystallized from heptane to obtain 6.7 g ofyellow needle-shaped crystalline 2,3-difluoro-4-ethoxyphenyltrans-4-(trans-4-n-propylcyclohexyl)cyclohexane-thiocarboxylate.

(Third step)

To a suspension prepared by suspending 8.5 g (47.4 mmol) ofN-bromosuccinimide in 50 ml of methylene chloride was added dropwise 6.9g of hydrogen fluoride-pyridine at −78° C. in 20 min and stirred as itwas for 10 min. To this reaction solution was added dropwise 40 ml ofsolution of 6.7 g (15.8 mmol) of 2,3- difluoro-4-ethoxyphenyltrans-4-(trans-4-n-propylcyclohexyl)cyclohexane-thiocarboxylate inmethylene chloride in 40 min and stirred as it was for 2 hours. Thereaction solution was poured into saturated aqueous sodium carbonatesolution to terminate the reaction and then the methylene chloride layerwas separated. The methylene chloride layer was washed with 10% aqueoussodium bisulfite solution and water in turn, and then dried overanhydrous magnesium sulfate. The solvent was distilled off under areduced pressure, and the residue thus obtained was purified by silicagel column chromatography (eluent: heptane) and further recrystallizedfrom heptane to obtain 4.4 g of the subjective compound. Data of variouskind of spectrums supported the structure of the compound describedabove.

¹⁹F-NMR (CDC13). δ (ppm): −79.4 (s, —CF₂O—). Mass spectrum: 452 (M⁺).

Compounds shown below can be prepared by selecting known procedures oforganic synthesis and using them in combination with reference to theprocedures described in Examples described above.

m = 1, n = 0 No. R¹ A¹ X¹ A² X² A⁴ Y¹ 1 C₃H₇

CO₂

OC₂H₅ 2 C₃H₇

CO₂

OC₂H₅ 3 C₃H₇

CO₂

OC₂H₅ 4 C₃H₇

CO₂

OCH₃ 5 C₃H₇

CO₂

OC₂H₅ 6 C₃H₇

CO₂

OC₃H₇ 7 C₅H₁₁

CO₂

OC₂H₅ 8 C₅H₁₁

CO₂

OC₂H₅ 9 C₅H₁₁

CO₂

OCH₃ 10 C₅H₁₁

CO₂

OC₂H₅ 11 C₅H₁₁

CO₂

OC₃H₇ 12 C₅H₁₁

CO₂

OCH₃ 13 C₅H₁₁

CO₂

OC₂H₅ 14 C₅H₁₁

CO₂

OC₃H₇ 15 C₃H₇

CO₂

OC₂H₅ 16 C₃H₇

CO₂

OC₂H₅ 17 C₃H₇

CO₂

OC₂H₅ 18 C₃H₇

CO₂

OCH₃ 19 C₃H₇

CO₂

OC₂H₅ 20 C₃H₇

CO₂

OC₃H₇ 21 C₅H₁₁

CO₂

OC₂H₅ 22 C₅H₁₁

CO₂

OC₂H₅ 23 C₅H₁₁

CO₂

OC₂H₅ 24 C₅H₁₁

CO₂

OCH₃ 25 C₅H₁₁

CO₂

OC₂H₅ 26 C₅H₁₁

CO₂

OC₃H₇ m = n = 1 No. R¹ A¹ X¹ A² X² A³ X³ A⁴ Y¹ 27 C₃H₇

—

CO₂

—

OC₂H₅ 28 C₃H₇

—

CO₂

—

OC₂H₅ 29 C₃H₇

—

CO₂

—

OC₂H₅ 30 C₃H₇

—

CO₂

—

OC₂H₅ 31 C₃H₇

—

CO₂

—

OCH₃ 32 C₃H₇

CO₂

—

OC₂H₅ 33 C₃H₇

CO₂

—

OC₂H₅ 34 C₃H₇

CO₂

—

OC₂H₅ 35 C₃H₇

CO₂

—

OC₂H₅ 36 C₅H₁₁

CO₂

—

OC₂H₅ 37 C₃H₇

CO₂

—

OC₂H₅ 38 C₃H₇

CO₂

—

OC₂H₅ 39 C₃H₇

CO₂

—

OC₂H₅ 40 C₃H₇

CO₂

—

OC₂H₅ 41 C₅H₁₁

CO₂

—

OC₃H₇ 42 C₃H₇

—

—

CO₂

OC₂H₅ 43 C₃H₇

—

—

CO₂

OCH₃ 44 C₅H₁₁

—

—

CO₂

OC₂H₅ 45 C₅H₁₁

—

—

CO₂

OC₃H₇ 46 C₃H₇

—

CO₂

OC₂H₅ 47 C₃H₇

—

CO₂

OCH₃ 48 C₅H₁₁

—

CO₂

OC₂H₅ 49 C₅H₁₁

—

CO₂

OC₃H₇ 50 C₃H₇

—

CO₂

OC₂H₅ 51 C₃H₇

—

CO₂

OCH₃ 52 C₅H₁₁

—

CO₂

OC₂H₅ 53 C₅H₁₁

—

CO₂

OC₃H₇ 54 C₃H₇

—

—

CO₂

OC₂H₅ 55 C₃H₇

—

—

CO₂

OCH₃ 56 C₅H₁₁

—

—

CO₂

OC₂H₅ 57 C₅H₁₁

—

—

CO₂

OC₃H₇ 58 C₃H₇

—

CO₂

OC₂H₅ 59 C₃H₇

—

CO₂

OCH₃ 60 C₅H₁₁

—

CO₂

OC₂H₅ 61 C₅H₁₁

—

CO₂

OC₃H₇ 62 C₃H₇

—

CO₂

OC₂H₅ 63 C₃H₇

—

CO₂

OCH₃ 64 C₅H₁₁

—

CO₂

OC₂H₅ 65 C₅H₁₁

—

CO₂

OC₃H₇ 66 C₃H₇

—

CO₂

OC₂H₅ 67 C₃H₇

—

CO₂

OCH₃ 68 C₅H₁₁

—

CO₂

OC₂H₅ 69 C₅H₁₁

—

CO₂

OC₃H₇ 70 C₃H₇

CO₂

OC₂H₅ 71 C₃H₇

CO₂

OCH₃ 72 C₅H₁₁

CO₂

OC₂H₅ 73 C₅H₁₁

CO₂

OC₃H₇ 74 C₃H₇

CO₂

OC₂H₅ 75 C₃H₇

CO₂

OCH₃ 76 C₅H₁₁

CO₂

OC₂H₅ 77 C₅H₁₁

CO₂

OC₃H₇ 78 C₃H₇

—

CO₂

OC₂H₅ 79 C₃H₇

—

CO₂

OCH₃ 80 C₅H₁₁

—

CO₂

OC₂H₅ 81 C₅H₁₁

—

CO₂

OC₃H₇ 82 C₃H₇

CO₂

OC₂H₅ 83 C₃H₇

CO₂

OCH₃ 84 C₅H₁₁

CO₂

OC₂H₅ 85 C₅H₁₁

CO₂

OC₃H₇ 86 C₃H₇

CO₂

OC₂H₅ 87 C₃H₇

CO₂

OCH₃ 88 C₅H₁₁

CO₂

OC₂H₅ 89 C₅H₁₁

CO₂

OC₃H₇ 90 C₃H₇

—

CO₂

OC₂H₅ 91 C₃H₇

—

CO₂

OC₂H₅ 92 C₃H₇

CO₂

OC₂H₅ 93 C₃H₇

CO₂

OC₂H₅ 94 C₃H₇

CO₂

OC₂H₅ 95 C₃H₇

CO₂

OC₂H₅ 96 C₅H₁₁

CO₂

OCH₃ 97 C₃H₇

—

CO₂

OC₂H₅ 98 C₃H₇

—

CO₂

OC₂H₅ 99 C₃H₇

CO₂

OC₂H₅ 100 C₃H₇

CO₂

OC₂H₅ 101 C₃H₇

CO₂

OC₂H₅ 102 C₃H₇

CO₂

OC₂H₅ 103 C₅H₁₁

CO₂

OC₃H₇ 104 C₃H₇

—

CO₂

OC₂H₅ 105 C₃H₇

—

CO₂

OC₂H₅ 106 C₃H₇

CO₂

OC₂H₅ 107 C₃H₇

CO₂

OC₂H₅ 108 C₃H₇

CO₂

OC₂H₅ 109 C₃H₇

CO₂

OC₂H₅ 110 C₅H₁₁

CO₂

OCH₃ 111 C₃H₇

—

CO₂

OC₂H₅ 112 C₃H₇

—

CO₂

OC₂H₅ 113 C₃H₇

CO₂

OC₂H₅ 114 C₃H₇

CO₂

OC₂H₅ 115 C₃H₇

CO₂

OC₂H₅ 116 C₃H₇

CO₂

OC₂H₅ 117 C₅H₁₁

CO₂

OC₃H₇ 118 C₃H₇

—

CO₂

OC₂H₅ 119 C₃H₇

—

CO₂

OC₂H₅ 120 C₃H₇

CO₂

OC₂H₅ 121 C₃H₇

CO₂

OC₂H₅ 122 C₃H₇

CO₂

OC₂H₅ 123 C₃H₇

CO₂

OC₂H₅ 124 C₅H₁₁

CO₂

OCH₃ 125 C₃H₇

—

CO₂

OC₂H₅ 126 C₃H₇

—

CO₂

OC₂H₅ 127 C₃H₇

CO₂

OC₂H₅ 128 C₃H₇

CO₂

OC₂H₅ 129 C₃H₇

CO₂

OC₂H₅ 130 C₃H₇

CO₂

OC₂H₅ 131 C₅H₁₁

CO₂

OC₃H₇ m = 1, n = 0 No. R¹ A¹ X¹ A² X² A⁴ Y¹ 132 C₃H₇

CF₂O

OC₂H₅ 133 C₃H₇

CF₂O

OC₂H₅ 134 C₃H₇

CF₂O

OC₂H₅ 135 C₃H₇

CF₂O

OCH₃ 136 C₃H₇

CF₂O

OC₂H₅ 137 C₃H₇

CF₂O

OC₃H₇ 138 C₅H₁₁

CF₂O

OC₂H₅ 139 C₅H₁₁

CF₂O

OC₂H₅ 140 C₅H₁₁

CF₂O

OC₂H₅ 141 C₅H₁₁

CF₂O

OCH₃ 142 C₅H₁₁

CF₂O

OC₂H₅ 143 C₅H₁₁

CF₂O

OC₃H₇ 144 C₃H₇

—

CF₂O

OC₂H₅ 145 C₃H₇

—

CF₂O

OC₂H₅ 146 C₃H₇

—

CF₂O

OC₂H₅ 147 C₃H₇

—

CF₂O

OCH₃ 148 C₃H₇

—

CF₂O

OC₂H₅ 149 C₃H₇

—

CF₂O

OC₃H₇ 150 C₅H₁₁

—

CF₂O

OC₂H₅ 151 C₅H₁₁

—

CF₂O

OC₂H₅ 152 C₅H₁₁

—

CF₂O

OC₂H₅ 153 C₅H₁₁

—

CF₂O

OCH₃ 154 C₅H₁₁

—

CF₂O

OC₂H₅ 155 C₅H₁₁

—

CF₂O

OC₃H₇ 156 C₃H₇

CF₂O

OC₂H₅ 157 C₃H₇

CF₂O

OC₂H₅ 158 C₃H₇

CF₂O

OC₂H₅ 159 C₃H₇

CF₂O

OCH₃ 160 C₃H₇

CF₂O

OC₂H₅ 161 C₃H₇

CF₂O

OC₃H₇ 162 C₅H₁₁

CF₂O

OC₂H₅ 163 C₅H₁₁

CF₂O

OC₂H₅ 164 C₅H₁₁

CF₂O

OC₂H₅ 165 C₅H₁₁

CF₂O

OC₂H₅ 166 C₅H₁₁

CF₂O

OC₂H₅ 167 C₅H₁₁

CF₂O

OC₂H₅ m = n = 1 No. R¹ A¹ X¹ A² X² A³ X³ A⁴ Y¹ 168 C₃H₇

—

CF₂O

—

OC₂H₅ 169 C₃H₇

—

CF₂O

—

OC₂H₅ 170 C₃H₇

—

CF₂O

—

OC₂H₅ 171 C₃H₇

—

CF₂O

—

OC₂H₅ 172 C₅H₁₁

—

CF₂O

—

OCH₃ 173 C₃H₇

CF₂O

—

OC₂H₅ 174 C₃H₇

CF₂O

—

OC₂H₅ 175 C₃H₇

CF₂O

—

OC₂H₅ 176 C₃H₇

CF₂O

—

OC₂H₅ 177 C₅H₁₁

CF₂O

—

OCH₃ 178 C₃H₇

CF₂O

—

OC₂H₅ 179 C₃H₇

CF₂O

—

OC₂H₅ 180 C₃H₇

CF₂O

—

OC₂H₅ 181 C₃H₇

CF₂O

—

OC₂H₅ 182 C₅H₁₁

CF₂O

—

OC₃H₇ 183 C₃H₇

—

CF₂O

OC₂H₅ 184 C₃H₇

—

CF₂O

OC₂H₅ 185 C₃H₇

—

CF₂O

OC₂H₅ 186 C₃H₇

—

CF₂O

OC₂H₅ 187 C₃H₇

—

CF₂O

OCH₃ 188 C₃H₇

CF₂O

OC₂H₅ 189 C₃H₇

CF₂O

OC₂H₅ 190 C₃H₇

CF₂O

OC₂H₅ 191 C₃H₇

CF₂O

OC₂H₅ 192 C₅H₁₁

CF₂O

OCH₃ 193 C₃H₇

CF₂O

OC₂H₅ 194 C₃H₇

CF₂O

OC₂H₅ 195 C₃H₇

CF₂O

OC₂H₅ 196 C₃H₇

CF₂O

OC₂H₅ 197 C₅H₁₁

CF₂O

OC₃H₇ 198 C₃H₇

—

CF₂O

—

OC₂H₅ 199 C₃H₇

—

CF₂O

—

OC₂H₅ 200 C₃H₇

—

CF₂O

—

OC₂H₅ 201 C₃H₇

—

CF₂O

—

OC₂H₅ 202 C₃H₇

—

CF₂O

—

OCH₃ 203 C₃H₇

CF₂O

—

OC₂H₅ 204 C₃H₇

CF₂O

—

OC₂H₅ 205 C₃H₇

CF₂O

—

OC₂H₅ 206 C₃H₇

CF₂O

—

OC₂H₅ 207 C₅H₁₁

CF₂O

—

OC₃H₇ 208 C₃H₇

CF₂O

—

OC₂H₅ 209 C₃H₇

CF₂O

—

OC₂H₅ 210 C₃H₇

CF₂O

—

OC₂H₅ 211 C₃H₇

CF₂O

—

OC₂H₅ 212 C₅H₁₁

CF₂O

—

OC₃H₇ 213 C₃H₇

—

—

CF₂O

OC₂H₅ 214 C₃H₇

—

—

CF₂O

OC₂H₅ 215 C₃H₇

—

CF₂O

OC₂H₅ 216 C₃H₇

—

CF₂O

OC₂H₅ 217 C₃H₇

—

CF₂O

OC₂H₅ 218 C₃H₇

—

CF₂O

OC₂H₅ 219 C₃H₇

—

—

CF₂O

OC₂H₅ 220 C₃H₇

—

—

CF₂O

OC₂H₅ 221 C₃H₇

—

CF₂O

OC₂H₅ 222 C₃H₇

—

CF₂O

OC₂H₅ 223 C₃H₇

—

CF₂O

OC₂H₅ 224 C₅H₁₁

—

CF₂O

OCH₃ 225 C₅H₁₁

—

CF₂O

OC₂H₅ 226 C₅H₁₁

—

CF₂O

OC₃H₇ 227 C₃H₇

—

—

CF₂O

OC₂H₅ 228 C₃H₇

—

—

CF₂O

OC₂H₅ 229 C₃H₇

—

CF₂O

OC₂H₅ 230 C₃H₇

—

CF₂O

OC₂H₅ 231 C₃H₇

—

CF₂O

OC₂H₅ 232 C₃H₇

—

CF₂O

OC₂H₅ 233 C₃H₇

—

—

CF₂O

OC₂H₅ 234 C₃H₇

—

—

CF₂O

OC₂H₅ 235 C₃H₇

—

CF₂O

OC₂H₅ 236 C₃H₇

—

CF₂O

OC₂H₅ 237 C₃H₇

—

CF₂O

OC₂H₅ 238 C₅H₁₁

—

CF₂O

OCH₃ 239 C₅H₁₁

—

CF₂O

OC₂H₅ 240 C₅H₁₁

—

CF₂O

OC₃H₇ 241 C₃H₇

—

CF₂O

OC₂H₅ 242 C₃H₇

—

CF₂O

OC₂H₅ 243 C₃H₇

CF₂O

OC₂H₅ 244 C₃H₇

CF₂O

OC₂H₅ 245 C₃H₇

CF₂O

OC₂H₅ 246 C₃H₇

CF₂O

OC₂H₅ 247 C₃H₇

—

CF₂O

OC₂H₅ 248 C₃H₇

—

CF₂O

OC₂H₅ 249 C₃H₇

CF₂O

OC₂H₅ 250 C₃H₇

CF₂O

OC₂H₅ 251 C₃H₇

CF₂O

OC₂H₅ 252 C₅H₁₁

CF₂O

OCH₃ 253 C₅H₁₁

CF₂O

OC₂H₅ 254 C₅H₁₁

CF₂O

OC₃H₇ 255 C₃H₇

—

CF₂O

OC₂H₅ 256 C₃H₇

—

CF₂O

OC₂H₅ 257 C₃H₇

CF₂O

OC₂H₅ 258 C₃H₇

CF₂O

OC₂H₅ 259 C₃H₇

CF₂O

OC₂H₅ 260 C₃H₇

CF₂O

OC₂H₅ 261 C₃H₇

—

CF₂O

OC₂H₅ 262 C₃H₇

—

CF₂O

OC₂H₅ 263 C₃H₇

CF₂O

OC₂H₅ 264 C₃H₇

CF₂O

OC₂H₅ 265 C₃H₇

CF₂O

OC₂H₅ 266 C₅H₁₁

CF₂O

OCH₃ 267 C₅H₁₁

CF₂O

OC₂H₅ 268 C₅H₁₁

CF₂O

OC₃H₇ 269 C₃H₇

—

CF₂O

OC₂H₅ 270 C₃H₇

—

CF₂O

OC₂H₅ 271 C₃H₇

CF₂O

OC₂H₅ 272 C₃H₇

CF₂O

OC₂H₅ 273 C₃H₇

CF₂O

OC₂H₅ 274 C₃H₇

CF₂O

OC₂H₅ 275 C₃H₇

—

CF₂O

OC₂H₅ 276 C₃H₇

—

CF₂O

OC₂H₅ 277 C₃H₇

CF₂O

OC₂H₅ 278 C₃H₇

CF₂O

OC₂H₅ 279 C₃H₇

CF₂O

OC₂H₅ 280 C₅H₁₁

CF₂O

OCH₃ 281 C₅H₁₁

CF₂O

OC₂H₅ 282 C₅H₁₁

CF₂O

OC₃H₇ 283 C₃H₇

—

CF₂O

OC₂H₅ 284 C₃H₇

—

CF₂O

OC₂H₅ 285 C₃H₇

CF₂O

OC₂H₅ 286 C₃H₇

CF₂O

OC₂H₅ 287 C₃H₇

CF₂O

OC₂H₅ 288 C₃H₇

CF₂O

OC₂H₅ 289 C₃H₇

—

CF₂O

OC₂H₅ 290 C₃H₇

—

CF₂O

OC₂H₅ 291 C₃H₇

CF₂O

OC₂H₅ 292 C₃H₇

CF₂O

OC₂H₅ 293 C₃H₇

CF₂O

OC₂H₅ 294 C₅H₁₁

CF₂O

OCH₃ 295 C₅H₁₁

CF₂O

OC₂H₅ 296 C₅H₁₁

CF₂O

OC₃H₇ m = n = 0 No. R¹ A¹ X¹ A⁴ Y¹ 297 C₃H₇

COO

OCH₃ 298 C₃H₇

COO

OC₂H₅ 299 C₃H₇

COO

OC₃H₇ 300 C₅H₁₁

COO

OCH₃ 301 C₅H₁₁

COO

OC₂H₅ 302 C₅H₁₁

COO

OC₃H₇ 303 C₃H₇

CF₂O

OC₂H₅ 304 C₃H₇

CF₂O

OCH₃ 305 C₃H₇

CF₂O

OC₂H₅ 306 C₃H₇

CF₂O

OC₃H₇ 307 C₅H₁₁

CF₂O

OC₂H₅ 308 C₅H₁₁

CF₂O

OCH₃ 309 C₅H₁₁

CF₂O

OC₂H₅ 310 C₅H₁₁

CF₂O

OC₃H₇

No.

311

— —

312

— —

313

— —

314

— —

315

— —

316

— —

317

— —

318

— —

319

— —

320

— —

321

— —

322

— —

323

— —

324

—

325

—

326

—

327

—

328

—

329

—

330

—

331

—

332

—

333

—

334

—

335

—

336

—

337

—

338

—

339

—

340

—

341

—

342

—

343

—

344

—

345

—

346

—

347

—

348

—

349

—

350

—

351

—

352

—

353

—

354

—

355

—

356

—

357

—

358

—

359

—

360

—

361

—

362

—

363

—

364

—

365

—

366

—

367

—

368

—

369

—

370

—

371

—

372

—

373

—

374

—

375

—

376

—

377

—

378

—

379

—

380

—

381

—

382

—

383

—

384

—

385

—

386

—

387

—

388

—

389

—

390

—

391

—

392

—

393

—

394

—

395

—

396

—

397

—

398

—

399

—

400

—

401

—

402

—

403

—

404

—

405

—

406

—

407

—

408

—

409

—

410

—

411

—

412

—

413

—

414

—

415

—

416

—

417

—

418

—

419

—

420

—

421

—

422

—

423

—

424

—

425

—

426

—

427

—

428

—

429

—

430

—

431

—

432

—

433

—

434

—

435

—

436

—

437

—

438

—

439

—

440

—

441

—

442

—

443

—

444

—

445

—

446

—

447

—

448

—

449

—

450

—

451

—

452

—

453

—

454

—

455

—

456

—

457

—

458

—

459

—

460

—

461

—

462

—

463

—

464

—

465

—

466

—

467

—

468

—

469

—

470

—

471

—

472

—

473

—

474

—

475

—

476

—

477

—

478

—

479

—

480

—

481

—

482

—

483

—

484

—

485

—

486

—

487

—

488

—

489

—

490

—

491

—

492

—

493

—

494

—

495

—

496

—

497

—

498

—

499

—

500

—

501

—

502

—

503

—

504

—

505

—

506

—

507

—

508

—

509

—

510

—

511

512

513

514

515

516

517

518

519

520

521

522

523

524

525

526

527

528

529

530

531

532

533

534

535

536

537

538

539

540

541

542

543

544

545

546

547

548

549

550

551

552

553

554

555

556

557

558

559

560

561

562

563

564

565

566

567

568

569

570

571

572

573

574

575

576

577

578

579

580

581

582

583

584

585

586

587

588

589

590

591

592

593

594

595

596

597

598

599

600

601

602

603

604

605

606

607

608

609

610

611

612

613

614

615

616

617

618

619

620

621

622

623

624

625

626

627

628

629

630

631

632

633

634

635

636

637

638

639

640

641

642

643

644

645

646

647

648

649

650

651

652

653

654

655

656

657

658

659

660

661

662

663

664

665

667

668

669

670

671

672

673

674

675

676

677

678

679

680

681

682

683

684

685

686

687

688

689

690

691

USE EXAMPLES

In the Use Examples shown below, value of dielectric anisotropy Δ∈ wasdetermined by using a TN cell (twisted nematic cell) having a cellthickness of 9 μm at 25° C.

EXAMPLE 9 (USE EXAMPLE 1)

Clearing point (Cp) of a nematic liquid crystal of liquid crystalcomposition (hereinafter referred to as mother liquid crystal A)comprising the following compounds each in the amount shown below

4-butoxyphenyl 4-(trans-4-propylcyclohexyl)carboxybenzoate 27.6% (byweight, the same unit is applied below)

4 -ethoxyphenyl 4- (trans-4-butylcyclohexyl) carboxybenzoate 20.7%

4-methoxyphenyl 4-(trans-4-pentylcyclohexyl)carboxybenzoate 20.7%

4-ethoxyphenyl 4- (trans-4-propylcyclohexyl) carboxybenzoate 17.2%

4-ethoxyphenyl 4-(trans-4-pentylcyclohexyl)carboxybenzoate 20 13.8% was74.6° C. and its Δ∈ was 0.0.

This mother liquid crystal A in an amount of 85 parts by weight wasmixed with 15 parts by weight of the 2,3-difluoro-4-ethoxyphenyl2-fluoro-4-(2-(trans-4-propylcyclohexyl)ethyl)-benzoate (Compound No.15) obtained in Example 1, and its physical properties were determined.Value of the physical properties of the compound obtained byextrapolation from the results were as follows:

Cp: 129.4° C., Δ∈: −4.17

EXAMPLE 10 (USE EXAMPLE 2)

Mother liquid crystal A in an amount of 90 parts by weight was mixedwith 10 parts by weight of 2,3-difluoro-4-ethoxyphenyl4-(2-(trans-4-pentylcyclohexyl)vinyl)cyclohexyl-carboxylate (CompoundNo. 7), and its physical properties were determined. Value of thephysical properties of the compound obtained by extrapolation from theresults were as follows:

Cp: 187.1° C., Δ∈: −5.67

EXAMPLE 11 (USE EXAMPLE 3)

Mother liquid crystal A in an amount of 85 parts by weight was mixedwith 15 parts by weight of the (2,3-difluoro-4-ethoxyphenyl)oxy(4-(trans-4-n-pentylcyclohexyl)phenyl) -difluoromethane (Compound No. 152)obtained in Example 2, and its physical properties were determined.Value of the physical properties of the compound obtained byextrapolation from the results were as follows:

Cp: 114.1° C., Δ∈: −4.20

EXAMPLE 12 (USE EXAMPLE 4)

Clearing point (Cp) of a nematic liquid crystal of liquid crystalcomposition (hereinafter referred to as mother liquid crystal B)comprising the following compounds each in the amount shown below

4-(trans-4-propylcyclohexyl)benzonitrile 24% (by weight, the same unitis applied below) 4-(trans-4-pentylcyclohexyl)benzonitrile 36%4-(trans-4-heptylcyclohexyl)benzonitrile 25%4-(4-propylphenyl)benzonitrile 15%

was 72.4° C. When this liquid crystal composition was filled in a TNcell (twisted nematic cell) having a cell thickness of 9 μm, its drivingthreshold voltage (Vth) was 1.78 V, value of dielectric anisotropy (Δ∈)was +11.0, value of optical anisotropy (Δn) was 0.137, and viscosity at20° C. (η₂₀) was 27.0 mPa·s.

This mother liquid crystal B in an amount of 85 parts by weight wasmixed with 15 parts by weight of thedifluoro-(4-(trans-4-propylcyclohexyl)phenyloxy)(4-(trans-4-pentylcyclohexyl)phenyl)methane (Compound No. 572) obtainedin Example 6, and its physical properties were determined. The resultswere as follows:

Cp: 90.3° C., Vth: 1.81 V, Δ∈: 9.9, Δn: 0.136, η₂₀: 28.4 mPa·s

Further, while this liquid crystal composition was left in a freezer at−20° C. for 25 days, separation of crystals or development of smecticphase was not noticed.

EXAMPLE 13 (USE EXAMPLE 5)

Mother liquid crystal B in an amount of 85 parts by weight was mixedwith 15 parts by weight ofdifluoro-(4-(trans-4-propylcyclohexyl)phenyloxy)(4-(2-(trans-4-propylcyclohexyl)-ethyl) phenyl)methane (Compound No.591), and its physical properties were determined. The results were asfollows:

Cp: 87.2° C., Vth: 1.85 V, Δ∈: 9.9, Δn: 0.137, 72₂₀: 28.2 mPa·s

Further, while this liquid crystal composition was left in a freezer at−20° C. for 25 days, separation of crystals or development of smecticphase was not noticed.

EXAMPLE 14 (USE EXAMPLE 6)

Mother liquid crystal B in an amount of 85 parts by weight was mixedwith 15 parts by weight of difluoro-(4-(trans-4-pentylcyclohexyl)phenyloxy) (4-(2-(trans-4-propylcyclohexyl) -ethyl)phenyl)methane(Compound No. 592), and its physical properties were determined. Theresults were as follows:

Cp: 89.8° C., Vth: 1.87 V, Δ∈: 9.7, Δn: 0.136, η₂₀ : 29.0 mPa·s

Further, while this liquid crystal composition was left in a freezer at−20° C. for 25 days, separation of crystals or development of smecticphase was not noticed.

EXAMPLE 15 (USE EXAMPLE 7)

Physical properties of the liquid crystal composition shown inComposition Example 1 were determined. As the results, Cp was 90.2 andΔ∈was 6.8.

EXAMPLE 16 (USE EXAMPLE 8)

Physical properties of the liquid crystal composition shown inComposition Example 2 were determined. As the results, Cp was 87.1 andΔ∈was 8.5.

EXAMPLE 17 (USE EXAMPLE 9)

Physical properties of the liquid crystal composition shown inComposition Example 3 were determined. As the results, Cp was 94.0 andΔ∈was 29.8.

EXAMPLE 18 (USE EXAMPLE 10)

Physical properties of the liquid crystal composition shown inComposition Example 4 were determined. As the results, Cp was 91.7 andΔ∈was 6.1.

EXAMPLE 19 (USE EXAMPLE 11)

Physical properties of the liquid crystal composition shown inComposition Example 5 were determined. As the results, Cp was 79.4 andΔ∈was 7.2.

EXAMPLE 20 (USE EXAMPLE 12)

Physical properties of the liquid crystal composition shown inComposition Example 6 were determined. As the results, Cp was 91.4 andΔ∈was 4.5.

EXAMPLE 21 (USE EXAMPLE 13)

Physical properties of the liquid crystal composition shown inComposition Example 7 were determined. As the results, Cp was 87.1 andΔ∈was 27.9.

EXAMPLE 22 (USE EXAMPLE 14)

Physical properties of the liquid crystal composition shown inComposition Example 8 were determined. As the results, Cp was 62.1 andΔ∈was 9.6.

EXAMPLE 23 (USE EXAMPLE 15)

Physical properties of the liquid crystal composition shown inComposition Example 9 were determined. As the results, Cp was 64.1 andΔ∈was 6.0.

EXAMPLE 24 (USE EXAMPLE 16)

Physical properties of the liquid crystal composition shown inComposition Example 10 were determined. As the results, Cp was 100.7 andΔ∈was 7.5.

EXAMPLE 25 (USE EXAMPLE 17)

Physical properties of the liquid crystal composition shown inComposition Example 11 were determined. As the results, Cp was 96.6 andΔ∈was 6.4.

EXAMPLE26 (USE EXAMPLE 18)

Physical properties of the liquid crystal composition shown inComposition Example 12 were determined. As the results, Cp was 79.8 andΔ∈was 6.2.

EXAMPLE 27 (USE EXAMPLE 19)

Physical properties of the liquid crystal composition shown inComposition Example 13 were determined. As the results, Cp was 94.5 andΔ∈was 3.8.

EXAMPLE 28 (USE EXAMPLE 20)

Physical properties of the liquid crystal composition shown inComposition Example 14 were determined. As the results, Cp was 99.8 andΔ∈was 4.6.

EXAMPLE 29 (USE EXAMPLE 21)

Physical properties of the liquid crystal composition shown inComposition Example 15 were determined. As the results, Cp was 88.5 andΔ∈was 2.9.

EXAMPLE 30 (USE EXAMPLE 22)

Physical properties of the liquid crystal composition shown inComposition Example 16 were determined. As the results, Cp was 86.5 andΔ∈was 5.4.

EXAMPLE 31 (USE EXAMPLE 23)

Physical properties of the liquid crystal composition shown inComposition Example 17 were determined. As the results, Cp was 73.8 andA c was 8.4.

EXAMPLE 32 (USE EXAMPLE 24)

Physical properties of the liquid crystal composition shown inComposition Example 18 were determined. As the results, Cp was 76.8 andΔ∈was 12.6.

EXAMPLE 33 (USE EXAMPLE 25)

Physical properties of the liquid crystal composition shown inComposition Example 19 were determined. As the results, Cp was 97.0 andΔ∈was 8.1.

EXAMPLE 34 (USE EXAMPLE 26)

Physical properties of the liquid crystal composition shown inComposition Example 20 were determined. As the results, Cp was 83.1 andΔ∈was 4.1.

EXAMPLE 35 (USE EXAMPLE 27)

Physical properties of the liquid crystal composition shown inComposition Example 21 were determined. As the results, Cp was 82.4 andΔ∈was −1.8.

EXAMPLE 36 (USE EXAMPLE 28)

Physical properties of the liquid crystal composition shown inComposition Example 22 were determined. As the results, Cp was 77.3 andΔ∈was −2.1.

EXAMPLE 37 (USE EXAMPLE 29)

Physical properties of the liquid crystal composition shown inComposition Example 23 were determined. As the results, Cp was 78.8 andΔ∈was −3.0.

In addition to the Examples shown above, the following Examples (UseExamples) can be shown. In the following Examples, compounds aredesignated by using symbols according to the definitions shown in Table1 described above, and T_(NI) indicates clearing point, η: viscosity,Δn: optical anisotropy value, Δ∈: dielectric anisotropy value, V_(th):threshold voltage, and P: pitch.

EXAMPLE 38 (USE EXAMPLE 30)

5-HBCF2OBH-3 3.0% 2-HB(F)OCF2BH 3.0% 1V2-BEB(F, F)-C 5.0% 3-HB-C 25.0%1-BTB-3 5.0% 2-BTB-1 10.0% 3-HH-4 11.0% 3-HHB-1 5.0% 3-HHB-3 9.0%3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F) TB-2 6.0%3-HB(F)TB-3 6.0% T_(NI) = 92.4 (° C.) η = 16.0 (mPa.s) Δn = 0.162 Δε =7.0 V_(th) = 2.12 (V)

Pitch of a liquid crystal composition prepared by adding 0.8 part byweight of optically active compound CM 33 to 100 parts by weight of theliquid crystal composition described above was as follows:

P=11 μm

EXAMPLE 39 (USE EXAMPLE31)

3-H2BCF2OBH-5 5.0% 3-HB(F, F)OCF2BH-5 5.0% 2O1-BEB(F)-C 5.0%3O1-BEB(F)-C 15.0% 4O1-BEB(F)-C 13.0% 5O1-BEB(F)-C 13.0% 2-HHB(F)-C15.0% 3-HHB(F)-C 15.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-44.0% 3-HHB-1 8.0% 3-HHB-O1 4.0% T_(NI) = 92.9 (° C.) η = 86.0 (mPa.s) Δn= 0.146 Δε = 29.7 V_(th) = 0.90 (V)

EXAMPLE 40 (USE EXAMPLE 32)

3-H2BCF2OBH-5 4.0% 3-HB(F, F)OCF2BH-5 4.0% 2-BEB-C 12.0% 3-BEB-C 4.0%4-BEB-C 6.0% 3-HB-C 28.0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 4.0%3-HEB-O2 6.0% 5-HEB-O2 5.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% T_(NI) = 67.8 (°C.) η = 28.2 (mPa.s) Δn = 0.115 Δε = 10.0 V_(th) = 1.35 (V)

EXAMPLE 41 (USE EXAMPLE 33)

5-HBCF2OBH-3 3.0% 3-H2BCF2OBH-3 3.0% 7-HB(F)-F 5.0% 5-H2B(F)-F 5.0%3-HB-O2 10.0% 3-HH-4 5.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HHB(F)-F10.0% 3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0%2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-1 2.0% 3-HHB-O1 5.0% 3-HHB-34.0% T_(NI) = 90.6 (° C.) η = 19.4 (mPa.s) Δn = 0.093 Δε = 3.2 V_(th) =2.67 (V)

EXAMPLE 42 (USE EXAMPLE 34)

3-H2BCF2OBH-3 4.0% 2-HB(F)OCF2BH-5 3.0% 5-HVHEB(2F, 3F)-O2 3.0% 7-HB(F,F)-F 3.0% 3-HB-O2 7.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HHB(F)-F10.0% 2-HBB(F)-F 9.0% 3-HBB(F)-F 9.0% 5-HBB(F)-F 6.0% 2-HBB-F 4.0%3-HBB-F 4.0% 5-HBB-F 3.0% 3-HBB(F, F)-F 5.0% 5-HBB(F, F)-F 10.0% T_(NI)= 93.0 (° C.) η = 24.1 (mPa.s) Δn = 0.113 Δε = 5.8 V_(th) = 1.99 (V)

EXAMPLE 43 (USE EXAMPLE 35)

5-HBCF2OBH-3 3.0% 3-H2BCF2OBH-5 3.0% 3-HB(F, F)OCF2BH-5 3.0% 7-HB(F,F)-F 4.0% 3-H2HB(F, F)-F 12.0% 4-H2HB(F, F)-F 10.0% 5-H2HB(F, F)-F 10.0%3-HHB(F, F)-F 10.0% 4-HHB(F, F)-F 5.0% 3-HH2B(F, F)-F 10.0% 5-HH2B(F,F)-F 6.0% 3-HBB(F, F)-F 12.0% 5-HBB(F, F)-F 12.0% T_(NI) = 81.4 (° C.) η= 28.8 (mPa.s) Δn = 0.079 Δε = 8.2 V_(th) = 1.61 (V)

EXAMPLE 44 (USE EXAMPLE 36)

2-HB(F)OCF2BH-5 4.0% 3-HB(F, F)OCF2BH-5 4.0% 3-HB-CL 10.0% 5-HB-CL 4.0%7-HB-CL 4.0% 1O1-HH-5 5.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F14.0% 4-HHB-CL 8.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0% 5-H2BB(F, F)-F9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0% T_(NI) = 90.5 (° C.) η = 22.9(mPa.s) Δn = 0.128 Δε = 4.7 V_(th) = 2.37 (V)

EXAMPLE 45 (USE EXAMPLE 37)

5-HBCF2OB(2F, 3F)-O2 15.0% 3-HEB-O4 24.0% 4-HEB-O2 17.0% 5-HEB-O1 17.0%3-HEB-O2 15.0% 5-HEB-O2 12.0% T_(NI) = 80.1 (° C.) η = 23.2 (mPa.s) Δn =0.092 Δε = −1.8

EXAMPLE 46 (USE EXAMPLE 38)

3-H2B(F)EB(2F, 3F)-O2 15.0% 3-HEB-O4 24.0% 4-HEB-O2 17.0% 5-HEB-O1 17.0%3-HEB-O2 15.0% 5-HEB-O2 12.0% T_(NI) = 82.4 (° C.) η = 29.1 (mPa.s) Δn =0.093

EXAMPLE 47 (USE EXAMPLE 39)

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O2 5.0% 3-HH-2 5.0% 3-HH-46.0% 3-HH-O1 4.0% 3-HH-O3 5.0% 5-HH-O1 4.0% 3-HB(2F, 3F)-O2 12.0%5-HB(2F, 3F)-O2 11.0% 3-HHB(2F, 3F)-O2 4.0% 5-HHB(2F, 3F)-O2 15.0%3-HHB(2F, 3F)-2 24.0% T_(NI) = 84.6 (° C.) Δn = 0.083 Δε = −3.9

EXAMPLE 48 (USE EXAMPLE 40)

5-HVHEB(2F, 3F)-02 5.0% 3-HH-5 5.0% 3-HH-4 5.0% 3-HH-O1 6.0% 3-HH-O36.0% 3-HB-O1 5.0% 3-HB-O2 5.0% 3-HB(2F, 3F)-O2 10.0% 5-HB(2F, 3F)-O210.0% 3-HHB(2F, 3F)-O2 12.0% 5-HHB (2F, 3F)-O2 8.0% 3-HHB(2F, 3F)-2 4.0%2-HHB(2F, 3F)-1 4.0% 3-HHEH-3 5.0% 3-HHEH-5 5.0% 4-HHEH-3 5.0% T_(NI) =88.5 (° C.) Δn = 0.079 Δε = −3.4

EXAMPLE 49 (USE EXAMPLE 41)

3-h2B(F)EB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O2 5.0% 3-BB(2F, 3F)-O212.0% 3-BB(2F, 3F)-O4 10.0% 5-BB(2F, 3F)-O4 10.0% 2-BB(2F, 3F)B-3 25.0%3-BB(2F, 3F)B-5 13.0% 5-BB(2F, 3F)B-5 14.0% 5-BB(2F, 3F)B-7 6.0% T_(NI)= 72.5 (° C.) Δn = 0.188 Δε = −3.6

EXAMPLE 50 (USE EXAMPLE 42)

5-HBCF2OBH-3 3.0% 3-H2B(F)EB(2F, 3F)-O2 4.0% 5-HVHEB(2F, 3F)-O2 4.0%5-HBCF2OB(2F, 3F)-O2 4.0% 3-BB(2F, 3F)-O2 10.0% 5-BB-5 9.0% 5-BB-O6 9.0%5-BB-O8 8.0% 1-BEB-5 3.0 & 3-BEB-5 3.0 & 5-BEB-5 3.0 & 3-HEB-02 20.0%5-BBB(2F,3F)-7 9.0% 3-H2BB(2F)-5 5.0% T_(NI) = 79.1 (° C.) Δn = 0.145 Δε= −3.1

EXAMPLE 51 (USE EXAMPLE 43)

3-H2BCF2OBH-5 3.0% 3-H2B(F)EB(2F, 3F)-O2 9.0% 5-HVHEB(2F, 3F)-O2 9.0%5-HBCF2OB(2F, 3F)-O2 9.0% 3-HB-O1 15.0% 3-HB-02 6.0% 3-HEB(2F, 3F)-O29.0% 4-HEB(2F,3F)-O2 9.0% 5-HEB(2F, 3F)-O2 4.0% 2-BB2B-02 6.0%1-B2BB(2F)-5 7.0% 5-B(3F)BB-O2 7.0% 3-BB(2F, 3F)B-3 7.0% T_(NI) = 84.5(° C.) Δn = 0.145 κ = 32.0 (mPa.s)

EXAMPLE 52 (USE EXAMPLE 44)

5-HVHEB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O2 3.0% 3-HB-O1 9.0% 3-HB-O29.0% 3-HB-O4 9.0% 2-BTB-O1 5.0% 1-BTB-O2 5.0% 3-BTB(2F, 3F)-O2 13.0%5-BTB (2F, 3F)-O2 13.0% 3-B(2F, 3F)TB(2F, 3F)-O4 4.0% 5-B(2F, 3F)TB(2F,3F)-O4 4.0% 3-HBTB-O1 5.0% 3-HBTB-O3 5.0% 3-HHB(2F, 3F)-O2 6.0%5-HBB(2F, 3F)-O2 4.0% 5-BPr(F)-O2 3.0% T_(NI) = 82.4 (° C.) Δn = 0.210

EXAMPLE 53 (USE EXAMPLE 45)

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O2 5.0% 3-HB-O2 10.0%5-HB-3 8.0% 5-BB(2F, 3F)-O2 10.0% 3-HB(2F, 3F)-O2 10.0% 5-HB(2F, 3F)-O28.0% 3-HHB (2F, 3F)-O2 7.0% 5-HHB(2F, 3F)-O2 4.0% 5-HHB (2F, 3F)-1O14.0% 2-HHB (2F, 3F)-1 5.0% 3-HBB-2 6.0% 3-BB (2F, 3F)B-3 8.0% 5-B2BB(2F, 3FOB-O2 10.0% T_(NI) = 69.9 (° C.) Δn = 0.143 Δε = −3.9

EXAMPLE 54 (USE EXAMPLE 46)

3-H2B(F)EB(2F, 3F)-O2 3.0% 5-HVHEB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O23.0% 3-HB-O2 20.0% 1O1-HH-3 6.0% 1O1-HH-5 5.0% 3-HH-EMe 12.0% 4-HEB-O19.0% 4-HEB-O2 7.0% 5-HEB-O1 8.0% 3-HHB-1 3.0% 4-HEB(2CN, 3CN)-O4 3.0%6-HEB(2CN, 3CN)-O4 3.0% 3-HEB(2CN, 3CN)-O5 4.0% 4-HEB(2CN, 3CN)-O5 3.0%5-HEB(2CN, 3CN)-O5 2.0% 2-HBEB(2CN, 3CN)-O2 2.0% 4-HBEB(2CN, 3CN)-O44.0% T_(NI) = 63.9 (° C.) Δn = 0.073 η = 43.3 (mPa.s) Δε = −5.7

EXAMPLE 55 (USE EXAMPLE 47)

3-H2B(F)EB(2F, 3F)-O2 5.0% 1V2-BEB(F, F)-C 5.0% 3-HB-C 20.0% V2-HB-C6.0% 1-BTB-3 5.0% 2-BTB-1 10.0% 1O1-HH-3 3.0% 3-HH-4 11.0% 3-HHB-1 11.0%3-HHB-3 3.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.6% 3-H2BTB-4 4.0% 3-HB(F)TB-26.0% 3-HHB-C 3.0% T_(NI) = 88.1 (° C.) η = 17.9 (mPa.s) Δn = 0.156 Δε =7.1 V_(th) = 2.09 (V)

Pitch of a liquid crystal composition prepared by adding 0.8 part byweight of optically active compound CM 33 to 100 parts by weight of theliquid crystal composition described above was as follows:

P=11.0 μm

EXAMPLE 56 (USE EXAMPLE 48)

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O2 5.0% 5-PyB-F 4.0%3-PyB(F)-F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0% 3-PyB-22.0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB-O83.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PYBB-F 6.0% 3-HHB-1 6.0% 3-HHB-3 3.0%2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-45.0% T_(NI) = 94.3 (° C.) η = 39.7 (mPa.s) Δn = 0.197 Δε = 6.6 V_(th) =2.23 (V)

EXAMPLE 57 (USE EXAMPLE 49)

3-H2B(F)EB(2F, 3F)-O2 3.0% 5-HVHEB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O23.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.0% 5O1-BEB(F)-C 4.0% 1V2-BEB(F,F)-C 10.0% 3-HEB-O4 4.0% 3-HH-EMe 6.0% 3-HB-O2 18.0% 7-HEB-F 2.0%3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0% 2O1-HBEB(F)-C 2.0%3-HB(F)EB(F)-C 2.0% 3-HBEB(F, F)-C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0%3-HEBEB-F 2.0% 3-HEBEB-1 2.0% 3-HHB(F)-C 4.0% T_(NI) = 78.3 (° C.) η =40.6 (mPa.s) Δn = 0.116 Δε = 24.3 V_(th) = 0.95 (V)

EXAMPLE 58 (USE EXAMPLE 50)

3-H2B(F)EB(2F, 3F)-O2 3.0% 5-HBCF2OB(2F, 3F)-O2 3.0% 7-HB(F) F 5.0%5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 5.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F10.0% 5-HHB(F)-F 10.0% 3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0%5-HBB(F)- 6.0% 2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-1 2.0% 3-HHB-O15.0% 3-HHB-3 4.0% T_(NI) = 85.2 (° C.) η = 25.9 (mPa.s) Δn = 0.093 Δε =3.4 V_(th) = 2.62 (V)

Pitch of a liquid crystal composition prepared by adding 0.3 part byweight of optically active compound CN to 100 parts by weight of theliquid crystal composition described above was as follows:

P=75 μm

EXAMPLE 59 (USE EXAMPLE 51)

5-HVHEB(2F, 3F)-O2 5.0% 3-HB-CL 10.0% 5-HB-CL 4.0% 7-HB-CL 4.0% 1O1-HH-55.0% 2-HBB(F)-F 8.0% 3-HBB(F)-F 8.0% 5-HBB(F)-F 14.0% 4-HHB-CL 8.0%5-HHB-CL 3.0% 3-H2HB(F)-CL 4.0% 3-HBB(F, F)-F 10.0% 5-H2BB(F, F)-F 9.0%3-HB(F)-VB-2 4.0% 3-H2BTB-2 4.0% T_(NI) = 91.2 (° C.) η = 20.8 (mPa.s)Δn = 0.128 Δε = 4.8 V_(th) = 2.35 (V)

EXAMPLE 60 (USE EXAMPLE 52)

3-H2BCF2OBH-3 2.0% 3-H2B(F)EB(2F, 3F)-O2 4.0% 5-HBCF2OB(2F, 3F)-O2 4.0%5-HB-F 12.0% 6-HB-F 9.0% 7-HB-F 7.0% 2-HHB-OCF3 2.0% 3-HHB-OCF3 7.0%4-HHB-OCF3 7.0% 3-HH2B-OCF3 4.0% 5-HH2B-OCF3 4.0% 3-HHB(F, F)-OCF3 5.0%3-HBB(F)-F 10.0% 3-HBB(F)-F 10.0% 3-HH2B(F)-F 3.0% 3-HB(F)BH-3 3.0%5-HBBH-3 3.0% 3-HHB(F, F)-OCF2H 4.0% T_(NI) = 87.2 (° C.) η = 18.6(mPa.s) Δn = 0.096 Δε = 4.6 V_(th) = 2.37 (V)

EXAMPLE 61 (USE EXAMPLE 53)

3-H2B(F)EB(2F, 3F)-O2 5.0% 5-HVHEB(2F, 3F)-O2 5.0% 5-HBCF2OB(2F, 3F)-O25.0% 2-HHB(F)-F 2.0% 3-HHB(F)-F 2.0% 5-HHB(F)-F 2.0% 2-HBB(F)-F 6.0%3-HBB(F)-F 6.0% 5-HBB(F)-F 10.0% 3-H2BB(F)-F 9.0% 3-HBB(F, F)-F 25.0%5-HBB(F, F)-F 19.0% 1O1-HBBH-4 2.0% 1O1-HBBH-5 2.0% T_(NI) = 94.7 (° C.)η = 31.6 (mPa.s) Δn = 0.131 Δε = 7.0 V_(th) = 1.95 (V)

COMPARATIVE EXAMPLES 1 and 2

As compounds to be compared with ones of the present invention, compound(c-1) described in Japanese Patent Publication No. Sho 62-39136 (R═C₃H₇,R′═CH₃) and compound (d-1) described in Japanese patent Publication No.Sho 62-46527 (R═C₅H₁₁, R′═C₃H₇, X═Y═H) were synthesized according to apreparation method described in each of the patent publications.

Mother liquid crystal B in an amount of 85 parts by weight and 15 partsby weight of compound (c-1), and 85 parts by weight of mother liquidcrystal B and 15 parts by weight of compound (d-1) were mixed,respectively, to prepare two liquid crystal compositions, and thephysical properties of the liquid crystal compositions were determined.Further, liquid crystal compositions thus prepared were left in separatefreezers each kept at −20° C., and miscibility was judged by countingthe number of days lapsed from the day when the compositions were put inthe freezer until the day when crystals separated (or smectic phasedeveloped) in the liquid crystal compositions. These results are showninTable 2 together with the results in Example 12 (Use Example 4)(numeral shown in the parentheses indicate the value of physicalproperties of each of the compounds obtained by extrapolation from themother liquid crystal).

TABLE 2 Cp(° C.) Δε η₂₀(mPa · s) Vth(V) Miscibil.*¹ Mother liquidcrystal B 72.4 11.0 27.5 1.78 >25 Com. Ex. 1 85.6 9.6 26.8 1.96 >25

(159.7) (2.3) (28.5) Com. Ex. 2 100.8 9.5 31.8 2.02  15

(261.7) (1.0) (59.0) — Ex. 12 90.3 9.9 28.4 1.81 >25

(191.7) (3.7) (33.5) — *¹Miscibility: Number of days lapsed from the daywhen the liquid crystal composition was left in a freezer at −20° C.until the day when crystals (solid such as smectic phase) separated.

In Comparative Example 1, whereas viscosity of the liquid crystalcomposition lowered compared with mother liquid crystal B, thresholdvoltage raised by 0.18 V. In Comparative Example 2, whereas it isdemonstrated that comparative compound (d-1) was remarkable thancompound (c-1) in the effect of raising clearing point, viscosity ofliquid crystal composition was higher than mother liquid crystal B, andas to the threshold voltage, its value raised by as large as 0.24 V. Insuch a way, although compounds (c-1) and (d-1) have a respective merit,they have a defect that threshold voltage becomes high, and thereby itcan be understood that the compounds can not be used for liquid crystalcompositions for low voltage driving. In contrast to the comparativecompounds, a compound of the present invention (Compound No. 572,Example 12) has an intermediate ability between compound (c-1) andcompound (d-1) in the effect of raising clearing point; exhibits such alow viscosity as that of three rings compound (c-1) despite of having afour rings structure; and to our surprise, exhibits almost the samethreshold voltage as mother liquid crystal B. That is, this compound canraise clearing point by nearly 20° C. by adding to mother liquid crystalB with hardly affecting threshold voltage.

Four rings compound (d-1) is very strong in smectogenecity, anddevelopment of its smectic phase was confirmed in a freezer at −20° C.in 15 days. In contrast to compound (d-1), separation of crystals wasnot noticed over 25 days with the compound of the present invention andthe present compound was confirmed to have considerably excellentmiscibility at low temperatures.

COMPERATIVE EXAMPLE 3

Mother liquid crystal B in an amount of 85 parts by weight was mixedwith 15 parts by weight of compound (c-1) to prepare a liquid crystalcomposition and its physical properties were determined. The results areshown in Table 3 together with the results in Example 9 (Use Example 1)to Example 11 (Use Example 3).

TABLE 3 Cp(° C.) Δε Mother liquid crystal A 74.6 0.0 Com. Ex. 3 160.71.4

Ex. 9 129.4 −4.17

Ex. 10 187.1 −5.67

Ex. 11 114.1 −4.20

In the value of negative dielectric anisotropy which is considered to beimportant in IPS driving, whereas the dielectric anisotropy valueobtained by extrapolation with the compound (c-1) was 1.4, the value ofthe compound of Examples 9, 10, and 11 exhibited remarkably as largenegative value as −4.17, −5.67, and −4.20, respectively. Further,whereas the clearing point obtained by extrapolation with compound (c-1)was 160.6, that of the compound of Examples 9, 10, and 11 were suchclosely resembled values as 129.4° C., 187.1° C., and 114.4° C.,respectively.

As described above, the liquid crystalline compounds of the presentinvention are very effective in largely reducing dielectric anisotropyvalue and have characteristics which can sufficiently cope with IPSdriving.

INDUSTRIAL APPLICABILITY

As will be clear from the examples and comparative examples describedabove, the liquid crystalline compounds of the present invention areexcellent in an overall balance of

1) effect of raising clearing point of liquid crystal compositions,

2) effect of lowering viscosity of liquid crystal compositions, and

3) effect of not lowering dielectric anisotropy (raising thresholdvoltage) of liquid crystal compositions; have a low viscosity andnegative large dielectric anisotropy; and have very usefulcharacteristics which can not be found in known liquid crystallinecompounds.

What is claimed is:
 1. A liquid crystalline compound expressed by thegeneral formula (1)

wherein R¹ represents an alkyl group having 1 to 20 carbon atoms one ormore non-adjacent methylene groups in the alkyl group may be replaced byoxygen atom, sulfur atom, or vinylene group; Y¹ represents an alkoxygroup having 1 to 19 carbon atoms; X¹ represents single bond,1,2-ethylene group, or vinylene group, X² represents single bond,1,2-ethylene group, vinylene group, or —COO—, and X³ represents —COO—,provided that at least one of X¹ and X² represents 1,2-ethylene group orvinylene group, and at least one of X² and X³ represents —COO—; ring A¹represents trans-1,4-cyclohexylene group, ring A², ring A³, and ring A⁴independently represent trans-1,4-cyclohexylene group CH₂ group on whichring may be replaced by oxygen atom, or 1,4-phenylene group one or morehydrogen atoms of which may be replaced by fluorine atom or chlorineatom, provided that at least one ring of ring A³ and ring A⁴ represents2,3-difluoro-1,4-phenylene group; and m and n are independently 0 or 1,provided that m+n is 1 or 2, when m=1, n=0, X¹ represents 1,2-ethylenegroup, and X² represents —COO—, then ring A² represents 1,4-phenylenegroup at least one hydrogen atom in which group is replaced by fluorineatom; when m=0, n=1, and X¹ represents 1,2-ethylene group, then ring A³represents 1,4-phenylene group at least one hydrogen atom in which groupis replaced by fluorine atom; when m=n=1, one of X¹ and X² represents1,2-ethylene group, and the other represents single bond, then ring A³represents 1,4-phenylene group at least one hydrogen atom in which groupis replaced by fluorine atom.
 2. The liquid crystalline compoundaccording to claim 1 wherein m=1, n=0, and X² is —COO— in the generalformula (1).
 3. The liquid crystalline compound according to claim 1wherein m=n=1 and X³ is —COO— in the general formula (1).
 4. The liquidcrystalline compound according to claim 2 wherein X¹ is 1,2-ethylenegroup and ring A² is 3-fluoro-1, 4-phenylene group in the generalformula (1).
 5. The liquid crystalline compound according to claim 2wherein X¹ is vinylene group and ring A² is 1,4-phenylene group in thegeneral formula (1).
 6. The liquid crystalline compound according toclaim 2 wherein X¹ is vinylene group and ring A² is 1,4-cyclohexylenegroup in the general formula (1).
 7. A liquid crystal compositioncomprising at least two components at least one of which is a liquidcrystalline compound expressed by the general formula (1) according toclaim
 1. 8. A liquid crystal composition comprising, as a firstcomponent, at least one liquid crystalline compound defined in any oneof claims 1, 2, 3, or 4-6, and as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one ormore non-adjacent methylene groups in the alkyl group may be replaced byoxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may bereplaced by fluorine atom; Y2 represents fluorine atom, chlorine atom,—OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L²independently represent hydrogen atom or fluorine atom; Z¹ and Z²independently represent 1,2-ethylene group, vinylene group, 1,4-butylenegroup, —COO—, —CF₂O—, —OCF₂—, or single bond; B representstrans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene grouphydrogen atom of which may be replaced by fluorine atom; and Crepresents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atomof which may be replaced by fluorine atom.
 9. A liquid crystalcomposition comprising, as a first component, at least one liquidcrystalline compound defined in any one of claims 1, 2, 3, or 4-6, andas a second component, at least one compound selected from the groupconsisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or vinylene group, and any hydrogenatom in the alkyl group may be replaced by fluorine atom; y3 representsCN group or —C≡C—CN; D represents trans-1,4-cyclohexylene,1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; Erepresents trans-1,4-cyclohexylene, 1,4-phenylene hydrogen atom of whichmay be replaced by fluorine atom, or pyrimidine-2,5-diyl group; F shownin the general formula (5) represents trans-1,4-cyclohexylene or1,4-phenylene group, and F in the general formula (6) representsfluorine atom; Z³ represents 1,2-ethylene group, —COO—, or single bond;L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom;and a, b, and c are independently 0 or
 1. 10. A liquid crystalcomposition comprising, as a first component, at least one liquidcrystalline compound defined in any one of claims 1, 2, 3, or 4-6, andas a second component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; K representstrans-1,4-cyclohexylene or 1,4-phenylene group; F in the generalformulas (10) to (12) represent fluorine atoms; and Z⁶ and Z⁷independently represent —CH₂CH₂—, —CH₂O—, or single bond.
 11. A liquidcrystal composition comprising one or more optically active compounds inaddition to the liquid crystal composition defined in claim
 7. 12. Aliquid crystal display device comprising the liquid crystal compositiondefined in claim
 7. 13. A liquid crystal composition comprising, as afirst component, at least one liquid crystalline compound defined in anyone of claims 1, 2, 3, or 4-6, and as a second component, at least onecompound selected from the group consisting of the compounds expressedby any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; G, I, and Jindependently represent trans-1,4-cyclohexylene or pyrimidine-2,5-diyl,or 1,4-phenylene group at least one hydrogen atom of which may bereplaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH—, or single bond.
 14. A liquid crystalcomposition comprising, as a first component, at least one liquidcrystalline compound defined in any one of claims 1, 2, 3, or 4-6, as asecond component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; G, I, and Jindependently represent trans-1,4-cyclohexylene or pyrimidine-2,5-diyl,or 1,4-phenylene group at least one hydrogen atom of which may bereplaced by fluorine atom; and formulas (7), (8), and (9) Z⁴ and Z⁵independently represent —C≡—C—, —COO—, —CH₂CH₂—, —CH═CH—, or singlebond, and as a third component, at least one compound selected from thegroup consisting of the compounds expressed by any one of the generalformulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; K representstrans-1,4-cyclohexylene or 1,4-phenylene group; F in the generalformulas (10) to (12) represent fluorine atoms; and Z⁶ and Z⁷independently represent —CH₂CH₂—, —CH₂O—, or single bond.
 15. A liquidcrystal composition comprising, as a first component, at least oneliquid crystalline compound defined in any one of claims 1, 2, 3, or4-6, as a second component, at least one compound selected from thegroup consisting of the compounds expressed by any one of the generalformulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one ormore non-adjacent methylene groups in the alkyl group may be replaced byoxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may bereplaced by fluorine atom; Y² represents fluorine atom, chlorine atom,—OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF_(3;) L¹ andL2 independently represent hydrogen atom or fluorine atom; Z¹ and Z²independently represent 1,2-ethylene group, vinylene group, 1,4-butylenegroup, —COO—, —CF₂O—, —OCF₂—, or single bond; B representstrans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene grouphydrogen atom of which may be replaced by fluorine atom; and Crepresents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atomof which may be replaced by fluorine atom, and as a third component, atleast one compound selected from the group consisting of the compoundsexpressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; G, I, and Jindependently represent trans-1,4-cyclohexylene or pyrimidine-2,5-diyl,or 1,4-phenylene group at least one hydrogen atom of which may bereplaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH—, or single bond.
 16. A liquid crystalcomposition comprising, as a first component, at least one liquidcrystalline compound defined in any one of claims 1, 2, 3, or 8-10, as asecond component, at least one compound selected from the groupconsisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or vinylene group, and any hydrogenatom in the alkyl group may be replaced by fluorine atom; Y³ representsCN group or —C≡C—CN; D represents trans-1,4-cyclohexylene,1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; Erepresents trans-1,4-cyclohexylene, 1,4-phenylene hydrogen atom of whichmay be replaced by fluorine atom, or pyrimidine-2,5-diyl group; Frepresents trans-1,4-cyclohexylene or 1,4-phenylene group; Z³ represents1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independentlyrepresent hydrogen atom or fluorine atom; and a, b, and c areindependently 0 or 1, and as a third component, at least one compoundselected from the group consisting of the compounds expressed by any oneof the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; G, I, and Jindependently represent trans-1,4-cyclohexylene or pyrimidine-2,5-diyl,or 1,4-phenylene group at least one hydrogen atom of which may bereplaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH—, or single bond.
 17. A liquid crystalcomposition comprising, as a first component, at least one liquidcrystalline compound defined in any one of claims 1, 2, 3, or 8-10, as asecond component, at least one compound selected from the groupconsisting of the compounds expressed by any one of the general formulas(2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms one ormore non-adjacent methylene groups in the alkyl group may be replaced byoxygen atom or —CH═CH—, and any hydrogen atom in the alkyl group may bereplaced by fluorine atom; y² represents fluorine atom, chlorine atom,—OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L²independently represent hydrogen atom or fluorine atom; Z¹ and Z²independently represent 1,2-ethylene group, vinylene group, 1,4-butylenegroup, —COO—, —CF₂O—, —OCF₂—, or single bond; B representstrans-1,4-cyclohexylene or 1,3-dioxane-2,5-diyl, or 1,4-phenylene grouphydrogen atom of which may be replaced by fluorine atom; and Crepresents trans-1,4-cyclohexylene, or 1,4-phenylene group hydrogen atomof which may be replaced by fluorine atom, as a third component, atleast one compound selected from the group consisting of the compoundsexpressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or vinylene group, and any hydrogenatom in the alkyl group may be replaced by fluorine atom; Y³ representsCN group or —C≡C—CN; D represents trans-1,4-cyclohexylene,1,4-phenylene, pyrimidine-2,5-diyl, or 1,3-dioxane-2,5-diyl group; Erepresents trans-1,4-cyclohexylene, 1,4-phenylene group hydrogen atom ofwhich may be replaced by fluorine atom, or pyrimidine-2,5-diyl group; Fshown in the general formula (5) represents trans-1,4-cyclohexylene or1,4-phenylene group, and F in the general formula (6) representsfluorine atom; Z³ represents 1,2-ethylene group, —COO—, or single bond;L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom;and a, b, and c are independently 0 or 1, and as a fourth component, atleast one compound selected from the group consisting of the compoundsexpressed by any one of the general formulas (7), (8), and (9)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10carbon atoms one or more non-adjacent methylene groups in the alkylgroup may be replaced by oxygen atom or —CH═CH—, and any hydrogen atomin the alkyl group may be replaced by fluorine atom; G, I, and Jindependently represent trans-1,4-cyclohexylene or pyrimidine-2,5-diyl,or 1,4-phenylene group at least one hydrogen atom of which may bereplaced by fluorine atom; and Z⁴ and Z⁵ independently represent —C≡C—,—COO—, —CH₂CH₂—, —CH═CH—, or single bond.